WO2008145615A2 - Aminoazoline and urea derivatives for combating animal pests - Google Patents

Aminoazoline and urea derivatives for combating animal pests Download PDF

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Publication number
WO2008145615A2
WO2008145615A2 PCT/EP2008/056377 EP2008056377W WO2008145615A2 WO 2008145615 A2 WO2008145615 A2 WO 2008145615A2 EP 2008056377 W EP2008056377 W EP 2008056377W WO 2008145615 A2 WO2008145615 A2 WO 2008145615A2
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alkyl
radicals
carry
group
compounds
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PCT/EP2008/056377
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French (fr)
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WO2008145615A3 (en
Inventor
Christopher Koradin
Markus Kordes
Ernst Baumann
Ronan Le Vezouet
Deborah L. Culbertson
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Basf Se
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Priority to CN200880017486A priority Critical patent/CN101677552A/en
Priority to EP08759977A priority patent/EP2120576A2/en
Priority to BRPI0811202-9A2A priority patent/BRPI0811202A2/en
Priority to US12/600,852 priority patent/US20100298138A1/en
Priority to JP2010508866A priority patent/JP2010527973A/en
Publication of WO2008145615A2 publication Critical patent/WO2008145615A2/en
Publication of WO2008145615A3 publication Critical patent/WO2008145615A3/en
Priority to IL201793A priority patent/IL201793A0/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/18—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/32—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing >N—CO—N< or >N—CS—N< groups directly attached to a cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/26—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C07C279/16—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/14—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/44—Nitrogen atoms not forming part of a nitro radical
    • C07D233/50—Nitrogen atoms not forming part of a nitro radical with carbocyclic radicals directly attached to said nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/28—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/18—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Definitions

  • the present invention relates to the use of aminoazoline and urea derivatives for combating animal pests.
  • the invention also relates to a method for controlling animal pests by using these compounds, to seed and to an agricultural and veterinary composition comprising said compounds and to specific azoline and urea derivatives.
  • 2-(lndan-2-ylamino)-oxazoline compounds and 2-(1 ,2,3,4-tetrahydronapht-2-ylamino)- oxazoline, -thiazoline and -imidazoline compounds are described in EP-A-0251453 as having useful 0C2-adrenergic properties and thus being useful in the treatment of hyper- or hypoglycaemia. A pesticidal activity of these compounds is not mentioned.
  • WO 2007/020377 describes the use of 2-(indan-1-ylamino)-thiazoline compounds and 2-(1 ,2,3,4-tetrahydronapht-1-ylamino)-thiazoline compounds for controlling insects, acarines, nematodes or molluscs.
  • the invention relates to the use of compounds of formula (I) or of a salt thereof for combating animal pests
  • Z is a group of the formulae (I I. A), (II. B) or (II. C)
  • n 0, 1 , 2, 3 or 4;
  • n 1 or 2;
  • # is the binding site to the remainder of the molecule
  • X is S, O or NR 5 ;
  • Y is S, O or NR 5a ;
  • T is -OR T1 , -SR T2 , -O-C(O)-R T3 , -O-C(S)-R T4 or -S-C(S)-R 15 ;
  • R T1 , R T2 , R T3 , R T4 and R T5 are selected from hydrogen
  • phenyl which may carry 1 , 2 or 3 substituents R Tc ; where the phenyl ring may also be fused to another phenyl ring or to a 5- or 6-membered saturated, partially unsaturated or aromatic 5- or 6-membered heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N and optionally 1 or 2 carbonyl groups as ring members, where the fused ring system may carry 1 , 2 or 3 substituents R Tc ; saturated, partially unsaturated or aromatic 5- or 6-membered heterocyclyl containing 1 , 2 or 3 heteroatoms selected from O, S and N and optionally 1 or 2 car- bonyl groups as ring members, which may carry 1 , 2 or 3 substituents R Td ; or
  • R T3 , R T4 and R T5 are NR T31 R T32 , where R T31 and R T32 , independently of each other, are selected from hydrogen, C-i-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the 3 last-mentioned groups may carry 1 , 2 or 3 substituents R Ta , Cs-C ⁇ -cycloalkyl, which may carry 1 , 2 or 3 substituents R Tb ; aryl and aryl-Ci-C4-alkyl, where the aryl moiety in the 2 last-mentioned groups may carry 1 , 2 or 3 substituents R Tc ; or
  • R T31 and R T32 together with the nitrogen atom to which they are bound form a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or aromatic bered heterocyclic containing 1 , 2 or 3 heteroatoms selected from O, S and N and optionally 1 or 2 carbonyl groups as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R Td ;
  • R 1 is selected from the group consisting of hydrogen, cyano, C-i-C ⁇ -alkyl, Ci-C ⁇ - haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C ⁇ -alkoxycarbonyl, Ci-C ⁇ - alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynylcarbonyl;
  • R 2a , R 2b are selected from the group consisting of hydrogen, formyl, CN, d-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C-i-C ⁇ -alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6- alkynylcarbonyl, C-i-C ⁇ -alkoxycarbonyl, (C-i-C ⁇ -alkyOthiocarbonyl, (Ci-C ⁇ - alkoxy)thiocarbonyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals R a2 ,
  • phenyl benzoyl, phenoxycarbonyl, benzyl, benzylcarbonyl, benzyloxycarbonyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, 5- or 6-membered hetarylmethyl, 5- or 6-membered hetarylcarbonyl, 5- or 6- membered hetarylmethylcarbonyl, wherein each of the 10 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R b2 , and wherein the 5- or 6-membered heteroaromatic ring in hetarylmethyl, hetarylcarbonyl and hetarylmethylcarbonyl contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, and wherein the 5- or 6- membered heterocyclic ring contains 1 , 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring members; or R 1 together with R 2a
  • R 1 together with R 2b may also be a bridging carbonyl group C(O);
  • R 2c and R 2d are selected from hydrogen, formyl, C-i-C ⁇ - alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, aryl, aryl-Ci-C 4 -alkyl, hetaryl, hetaryl-Ci-C 4 - alkyl, C-i-C ⁇ -alkylcarbonyl, C-i-C ⁇ -alkylthiocarbonyl, C2-C6-alkenylcarbonyl, C2-C6- alkynylcarbonyl, Ci-C ⁇ -alkoxycarbonyl, Ci-C ⁇ -alkoxythiocarbonyl, arylcarbonyl, hetarylcarbonyl, aryloxycarbonyl and hetaryloxycarbonyl, where the aliphatic, aromatic or heteroaromatic moieties in the 17 last-mentioned radicals may carry 1 , 2, 3, 4
  • R 3a , R 3b , R 3c , R 3d independently of each other, are selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, d-C ⁇ -haloalkyl,
  • R 4a , R 4b independently of each other, are selected from the group consisting of hydrogen, halogen, C-i-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C-i-C ⁇ -haloalkyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals
  • each of the four last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R b4 , and wherein the 5 or 6 membered heteroaromatic ring in hetarylmethyl and hetaryl contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members; or
  • R 4a together with R 4b may also be C2-Cs-alkandiyl which may carry 1 , 2, 3, 4, 5 or 6 substituents R 41 and where one or two methylene groups of the C2-Cs-alkandiyl radical may be replaced by 1 or 2 non-adjacent heteroatoms or heteroatom- containing groups selected from O, S and NR 42 ; or
  • R 2a together with R 4a may form a bridging bivalent radical selected from the group con- sisting of C(O)-C(R 24a )(R 24b ), C(S)-C(R 24a )(R 24b ), CH 2 -C(R 24a )(R 24b ), S(O) 2 -
  • R 4c , R 4d are independently defined like R 4a and R 4b ;
  • R 5 , R 5a independently of each other, are selected from the group consisting of hydrogen, formyl, CN, Ci-C ⁇ -alkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl, Ci-C ⁇ -alkylcarbonyl, C 2 -C6-alkenylcarbonyl, C 2 -C6-alkynylcarbonyl, Ci-C ⁇ -alkoxycarbonyl, Ci-C ⁇ - alkylthiocarbonyl, wherein the carbon atoms in the aliphatic radicals of the afore- mentioned groups may carry any combination of 1 , 2 or 3 radicals R a5 ,
  • phenyl, benzyl, phenoxycarbonyl, 5 or 6 membered hetarylmethyl, 5 or 6 mem- bered hetarylcarbonyl and benzoyl each of the last six mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R b5 , and wherein the 5 or 6 membered heteroaromatic ring in hetarylmethyl and hetarylcarbonyl contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members;
  • each R Z1 is independently selected from the group consisting of halogen, OH, SH, SO 3 H, COOH, cyano, nitro, d-Ce-alkyl, d-Ce-alkoxy, d-Ce-alkylthio, C 2 -C 6 - alkenyl, C 2 -C6-alkenyloxy, C 2 -C6-alkenylthio, C 2 -C6-alkynyl, C 2 -C6-alkynyloxy, C 2 - C ⁇ -alkynylthio, Ci-C ⁇ -alkylsulfonyl, Ci-C ⁇ -alkylsulfoxyl, C 2 -C6-alkenylsulfonyl, C 2 - Ce-alkynylsulfonyl, a radical NR a R b , formyl, d-Ce-alkylcarbonyl, C 2 -C 6 - alken
  • L is a single bond, oxygen, sulfur or Ci-C6-alkandiyl, wherein one carbon might be replaced by oxygen
  • Cy is selected from the group consisting of C3-Ci2-cycloalkyl, which is unsubstituted or substituted with any combination of 1 , 2, 3, 4 or 5 radicals R bz , phenyl, naphthyl and mono- or bicyclic 5- to 10-membered heterocyclyl, which contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring mem- bers, wherein Cy is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R bz ;
  • radicals R Z1 that are bound to adjacent carbon atoms may form together with said carbon atoms a fused benzene ring, a fused saturated or par- tially unsaturated 5, 6, or 7 membered carbocycle or a fused 5, 6, or 7 membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals R bz ;
  • R a , R b are independently of each other selected from the group consisting of hydrogen, Ci-C ⁇ -alkyl, phenyl, benzyl, 5 or 6 membered hetaryl, C2-C6-alkenyl, or C2-C6- alkynyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals R aw ;
  • R c has one of the meanings given for R a and R b or is selected from the group consisting of Ci-C ⁇ -alkoxy, OH, NH2, Ci-C ⁇ -alkylamino, di(Ci-C6-alkyl)amino, arylamino, N-(Ci-C6-alkyl)-N-arylamino and diarylamino, wherein aryl is phenyl which may be unsubstituted or may carry 1 , 2 or 3 substituents R bc ;
  • R d , R e have one of the meanings given for R a and R b or are independently of each other selected from d-C ⁇ -alkoxy or di(Ci-C6-alkyl)amino.
  • R a2 , R a3 , R a4 , R a5 , R aw and R az are independently of each other selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C3-C6- cycloalkyl, Ci-C ⁇ -alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy,
  • Ci-C ⁇ -alkylcarbonyl Ci-C ⁇ -alkoxycarbonyl, d-C ⁇ -alkylthio, d-C ⁇ -haloalkylthio, Ci-C ⁇ -alkylsulfonyl and Ci-C ⁇ -haloalkylsulfonyl;
  • R b1 , R b2 , R b3 , R b4 , R b5 , R bc , R bz and R c2 are independently of each other selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C-i-Ce-alkyl, Ci-C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, d-Ce-alkoxy, C 2 -C 6 - alkenyloxy, C2-C6-alkynyloxy, d-C ⁇ -haloalkoxy, Ci-C6-alkylthio, C1-C6- alkylamino, di(Ci-C6-alkyl)amino, Ci-C ⁇ -alkylsulfonyl, d-C ⁇ -alkylsulfoxyl, formyl, Ci-C ⁇ -alkylcarbonyl, Ci-
  • R 22 , R 42 independently are hydrogen, d-C ⁇ -alkyl, C2-C6-alkenyl, d-C ⁇ -alkynyl, where the 3 last-mentioned groups may carry 1 , 2 or 3 substituents R a42 , C3-C6- cycloalkyl, which may carry 1 , 2 or 3 substituents R b42 ; aryl and aryl-Ci-C4-alkyl, where aryl moiety in the 2 last-mentioned groups may carry 1 , 2 or 3 substituents R c42 ;
  • each R Ta is independently selected from the group consisting of halogen, C3-C6- cycloalkyl, Cs-C ⁇ -halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, C1-C4- alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, C1-C4- haloalkylcarbonyloxy, phenyl, phenyloxy, phenylthio and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the four last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl
  • each R Tb is independently selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-C ⁇ -cycloalkyl, Cs-C ⁇ -halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Cs-C ⁇ -cycloalkoxy, C1-C4- alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, C1-C4- haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, Ci-C4-haloalkylcarbonyloxy, phenyl, phenyloxy, phenylthio and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the four
  • each R Tc is independently selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-C ⁇ -cycloalkyl, Cs-C ⁇ -halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl, C1-C4- haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl, C1-C4- alkylcarbonyloxy, d ⁇ -haloalkylcarbonyloxy, phenyl, phenyloxy, phenylthio and
  • each R Td is independently selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-C ⁇ -cycloalkyl, Cs-C ⁇ -halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl, C1-C4- haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl, C1-C4- alkylcarbonyloxy, phenyl, phenyloxy, phenylthio and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the four last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci
  • R a42 is independently defined like R Ta ;
  • R b42 is independently defined like R Tb ;
  • R c42 is independently defined like R Tc .
  • Another object of the present invention is an agricultural composition containing at least one compound of the formula (I) as defined above and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
  • Another object of the present invention is a veterinary composition containing at least one compound of the formula (I) as defined above and/or a veterinarily acceptable salt thereof and at least one veterinarily acceptable liquid or solid carrier.
  • the present invention also provides a method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a plant, seed, soil, area, material or environment in which the pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of the formula I or a salt thereof or a composition as defined above.
  • the invention further related to a method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally effective amount of a compound of the formula (I) or a veterinally acceptable salt thereof as defined above.
  • Bringing the animal in contact with the compound (I), its salt or the veterinary composition of the invention means applying or ad- ministering it to the animal.
  • a further object of the present invention is seed, comprising at least one compound of formula (I) and/or an agriculturally acceptable salt thereof.
  • Object of the invention are furthermore azoline compounds of the general formula I as defined above and salts thereof, except for compounds wherein n is 0, or n is 1 or 2 with R Z1 being d-C ⁇ -alkyl, d-C ⁇ -alkoxy or halogen, Z is a group of formula (I I. A) or (II. B) and R 2a , R 2b , R 4a , R 4b , R 4c and R 4d are all hydrogen.
  • Object of the invention are also azoline compounds of the general formula I as defined above and salts thereof, except for compounds wherein n is 0 or n is 1 or 2 with R Z1 being d-C ⁇ -alkyl, d-C ⁇ -alkoxy, halogen, phenyl or naphthyl, and simultaneously Z is a group of formula (II. A) or (II. B), R 2a , R 2b , R 3a , R 3b , R 3c and R 3d are all hydrogen and one of R 4a and R 4b is hydrogen and the other is hydrogen or d-C ⁇ -alkyl and one of R 4c and R 4d is hydrogen and the other is hydrogen or Ci-C6-alkyl.
  • the present invention relates to azoline compounds of the general formula I as defined above and salts thereof, except compounds wherein R 2a and R 2b are both hydrogen.
  • the present invention also relates to azoline compounds of the general formula I as defined above and salts thereof, except compounds wherein R 4a , R 4b , R 4c and R 4d are all hydrogen.
  • the present invention relates to azoline compounds of the general formula I as defined above and salts thereof, except compounds wherein n is 0 or n is 1 or 2 and R Z1 is d-C ⁇ -alkyl, d-C ⁇ -alkoxy or halogen.
  • the carbon atom which carries the radical R 1 creates a center of chirality. If there is no mirror plane ⁇ through this atom, which is for example the case when m is 2 and/or at least one of R 4a , R 4b , R 4c and R 4d is not hydrogen, the saturated cycle however not being symmetrically substituted, and/or n is not 0, the phenyl ring however not being symmetrically substituted, the compound (I) can be present in the form of different enantiomers or diastereomers, depending on the substitu- ents. In case Z is of the formula (II.
  • the present invention relates to every possible stereoisomer of the compounds of general formula (I), i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
  • Salts of the compounds of the formula (I) are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula (I) with a suitable base.
  • Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention.
  • Suit- able cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH 4 + ) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci- C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammo- nium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl- ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl- triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4- alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and bu- tyrate. They can be formed by reacting a compound of formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Suitable acid addition salts e.g. formed by compounds of formula ()l containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hy- drochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • inorganic acids for example hy- drochlorids, sulphates, phosphates, and nitrates
  • salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -Cm indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
  • Ci-C4-alkyl examples are methyl, ethyl, propyl, 1- methylethyl (isopropyl), butyl, 1-methylpropyl (sec-butyl, 2-butyl), 2-methylpropyl (iso- butyl), and 1 ,1-dimethylethyl (tert-butyl).
  • Ci-C ⁇ -alkyl further encompass pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl- 2-methylpropyl.
  • Ci-C ⁇ -haloalkyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C4-haloalkyl, such as chloromethyl, bromomethyl, di- chloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-
  • Examples for C1-C4- alkoxy include methoxy, ethoxy, OCH2-C2H5 (propoxy), OCH(CH3)2 (isopropoxy), n- butoxy, OCH(CH 3 )C 2 H 5 (sec-butoxy), OCH 2 CH(CHs) 2 (isobutoxy) and OC(CHs) 3 (tert- butoxy).
  • Ci-C ⁇ -alkoxy further encompass n-pentoxy, 1-methylbutoxy, 2- methylbutoxy, 3-methylbutoxy, 1 ,1-dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2- dimethyl-propoxy, 1 -ethyl propoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3- methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3- dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1- ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1-ethyl-1- methylpropoxy, 1-ethyl-2-methylpropoxy and the like.
  • Ci-C ⁇ -haloalkoxy refers to a Ci-C6-alkoxy group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • Ci-C4-haloalkoxy groups i.e.
  • C1-C4- alkoxy groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2- chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2- trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2,2- difluoropropoxy,
  • Ci-C ⁇ - haloalkoxy further encompass 5-fluoro-1-pentoxy, 5-chloro-1-pentoxy, 5-bromo-1- pentoxy, 5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1- hexoxy, 6-chloro-1-hexoxy, 6-bromo-1-hexoxy, 6-iodo-1-hexoxy, 6,6,6-trichloro-1- hexoxy and dodecafluorohexoxy.
  • Particularly preferred are chloromethoxy, fluorometh- oxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2- trifluoroethoxy.
  • Ci-Ce-alkoxy-Ci-C ⁇ -alkyl refers to d-C ⁇ -alkyl wherein 1 carbon atom carries a Ci-C ⁇ -alkoxy radical as mentioned above.
  • Examples are CH2OCH3, CH2-OC2H5, n-propoxymethyl, CH2-OCH(CH3)2, n-butoxymethyl, (1-methylpropoxy)- methyl, (2-methylpropoxy)methyl, CH 2 -OC(CH 3 )S, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2- (n-propoxy)-ethyl, 2-(1-methylethoxy)-ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)- ethyl, 2-(2-methylpropoxy)-ethyl, 2-(1 ,1-dimethylethoxy)-ethyl, 2-(methoxy)-propyl, 2- (ethoxy)-
  • Ci-C4-alkylcarbonyl examples include C(O)CH3, C(O)C 2 H 5 , n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1- methylpropylcarbonyl, 2-methylpropylcarbonyl and 1 ,1-dimethylethylcarbonyl.
  • Ci-C ⁇ -alkylcarbonyl further encompass n-pentylcarbonyl, 1- methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1 ,1- dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl, 2,2-dimethylpropylcarbonyl, 1- ethylpropylcarbonyl, n-hexylcarbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1 ,1-dimethylbutylcarbonyl, 1 ,2- dimethylbutylcarbonyl, 1 ,3-dimethylbutylcarbonyl, 2,2-dimethylbutylcarbonyl, 2,3- dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2- ethyl
  • Examples include chloromethylcarbonyl, bromomethylcarbonyl, dichloromethylcarbonyl, trichloromethyl- carbonyl, fluoromethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl, chloro- fluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 1- chloroethylcarbonyl, 1-bromoethylcarbonyl, 1-fluoroethylcarbonyl, 2- fluoroethylcarbonyl, 2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, 2-chloro-2- fluoroethylcarbonyl, 2-chloro-2,2-difluoroethylcarbonyl, 2,2-dichloro-2- fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, pentafluoroethyl
  • Ci-C 4 -alkoxycarbonyl examples include C(O)OCH 3 , C(O)OC 2 H 5 , C(O)O-CH 2 -C 2 H 5 , C(O)OCH(CHs) 2 , n-butoxycarbonyl, C(O)OCH(CH 3 )- C 2 H 5 , C(O) OCH 2 CH(CHs) 2 and C(O) OC(CH 3 )s.
  • Examples for d-Ce-alkoxycarbonyl further encompass n-pentoxycarbonyl, 1-methylbutoxycarbonyl, 2- methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1- ethylpropoxycarbonyl, n-hexoxycarbonyl, 1 ,1-dimethylpropoxycarbonyl, 1 ,2- dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3- methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1 ,1-dimethylbutoxycarbonyl, 1 ,2- dimethylbutoxycarbonyl, 1 ,3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2,3- dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2- ethylbutoxycarbonyl, 1 ,1 ,2-trimethylprop
  • Examples include chloro- methoxycarbonyl, bromomethoxycarbonyl, dichloromethoxycarbonyl, trichloromethoxy- carbonyl, fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, chlorofluoromethoxycarbonyl, dichlorofluoromethoxycarbonyl, chlorodifluoromethoxy- carbonyl, 1-chloroethoxycarbonyl, 1-bromoethoxycarbonyl, 1-fluoroethoxycarbonyl, 2- fluoroethoxycarbonyl, 2,2-difluoroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 2- chloro-2-fluoroethoxycarbonyl, 2-chloro-2,2-difluoroethoxycarbonyl, 2,2-dichloro-2- fluoroethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, pentafluoroeth
  • Examples for C1-C4- alkylcarbonyloxy include O-CO-CH3, O-CO-C2H5, n-propylcarbonyloxy, 1 -methylethylcarbonyloxy, n-butylcarbonyloxy, 1 -methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy and 1 ,1-dimethylethylcarbonyloxy.
  • Ci-C ⁇ - alkylcarbonyloxy further encompass n-pentylcarbonyloxy, 1-methylbutylcarbonyloxy, 2- methylbutylcarbonyloxy, 3-methylbutylcarbonyloxy, 1 ,1-dimethylpropylcarbonyloxy or 1 ,2-dimethylpropylcarbonyloxy.
  • Ci-C4-haloalkylcarbonyloxy examples include chloromethylcarbonyloxy, bromomethylcarbonyloxy, dichloromethylcarbonyloxy, trichloromethylcarbonyloxy, fluoromethylcarbonyloxy, difluoromethylcarbonyloxy, trifluoromethylcarbonyloxy, chlorofluoromethylcarbonyloxy, dichlorofluoromethylcarbonyoxyl, chlorodifluoromethyl- carbonyloxy, 1-chloroethylcarbonyloxy, 1-bromoethylcarbonyloxy, 1- fluoroethylcarbonyloxy, 2-fluoroethylcarbonyloxy, 2,2-difluoroethylcarbonyloxy, 2,2,2- trifluoroethylcarbonyloxy, 2-chloro-2-fluoroethylcarbonyloxy, 2-chloro-2,2- difluoroethylcarbonyloxy, 2,2-dichloro-2-fluoroeth
  • d-C ⁇ -alkylthio (Ci-C ⁇ -alkylsulfanyl: C-i-C ⁇ -alkyl-S-)
  • Ci-C4-alkylthio examples include methylthio, ethylthio, propylthio, 1- methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1 ,1- dimethylethylthio.
  • Examples for d-C ⁇ -alkylthio further encompass n-pentylthio, 1- methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1- ethylpropylthio, n-hexylthio, 1 ,1-dimethylpropylthio, 1 ,2-dimethylpropylthio, 1- methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1 ,1- dimethylbutylthio, 1 ,2-dimethylbutylthio, 1 ,3-dimethylbutythio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutlthio, 2-ethylbutylthio, 1 ,1 ,2- trimethylpropyl
  • Ci-C ⁇ -haloalkylthio refers to a d-C ⁇ -alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • Ci-C4-haloalkylthio groups i.e.
  • C1-C4- alkylthio groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoro- methylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2- fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2- difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2- difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trich
  • Ci-C ⁇ - haloalkylthio further encompass 5-fluoro-1-pentylthio, 5-chloro-1-pentylthio, 5-bromo-1- pentylthio, 5-iodo-1-pentylthio, 5,5,5-trichloro-1-pentylthio, undecafluoropentylthio, 6- fluoro-1-hexylthio, 6-chloro-1-hexylthio, 6-bromo-1-hexylthio, 6-iodo-1-hexylthio, 6,6,6- trichloro-1-hexylthio and dodecafluorohexylthio.
  • chloromethyl- thio particularly preferred are chloromethyl- thio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, 2-fluoroethylthio, 2- chloroethylthio and 2,2,2-trifluoroethylthio.
  • Ci-C4-alkylthiocarbonyl examples include C(O)SCHs, C(OSC2H 5 , C(O)-SCH 2 -C 2 H 5 , C(O)SCH(CHs) 2 , n-butylthiocarbonyl, C(O)SCH(CHs)-C 2 H 5 , C(O)SCH 2 CH(CHs) 2 and C(O)SC(CH 3 )s.
  • Examples for d-Ce-alkylthiocarbonyl further encompass n-pentylthiocarbonyl, 1-methylbutylthiocarbonyl, 2-methylbutylthiocarbonyl, 3-methylbutylthiocarbonyl, 2,2-dimethylpropylthiocarbonyl, 1-ethylpropylthiocarbonyl, n- hexylthiocarbonyl, 1 ,1-dimethylpropylthiocarbonyl, 1 ,2-dimethylpropylthiocarbonyl, 1- methylpentylthiocarbonyl, 2-methylpentylthiocarbonyl, 3-methylpentylthiocarbonyl, 4- methylpentylthiocarbonyl, 1 ,1-dimethylbutylthiocarbonyl, 1 ,2-dimethylbutylthiocarbonyl, 1 ,3-dimethylbutythiocarbonyl, 2,2-dimethylbutylthiocarbonyl, 2,3
  • Ci-C4-alkoxythiocarbonyl examples include C(S)OCHs, C(S)OC 2 H 5 , C(S)O-CH 2 -C 2 H 5 , C(S)OCH(CHs) 2 , n-butoxythiocarbonyl, C(S)OCH(CHs)-C 2 H 5 , C(S)OCH 2 CH(CHs) 2 and C(S) OC(CH 3 )s.
  • Examples for d-Ce-alkoxythiocarbonyl further encompass n-pentoxythiocarbonyl, 1-methylbutoxythiocarbonyl, 2- methylbutoxythiocarbonyl, 3-methylbutoxythiocarbonyl, 2,2- dimethylpropoxythiocarbonyl, 1-ethylpropoxythiocarbonyl, n-hexoxythiocarbonyl, 1 ,1- dimethylpropoxythiocarbonyl, 1 ,2-dimethylpropoxythiocarbonyl, 1-methylpentoxythiocarbonyl, 2-methylpentoxythiocarbonyl, 3- methylpentoxythiocarbonyl, 4-methylpentoxythiocarbonyl, 1 ,1- dimethylbutoxythiocarbonyl, 1 ,2-dimethylbutoxythiocarbonyl, 1 ,3-dimethylbutoxythiocarbonyl, 2,2-dimethylbutoxythiocarbonyl, 2,3- dimethylbutoxythiocarbonyl, 3,3-dimethylbutoxythi
  • Exam- pies for Ci-C 4 -alkylsulfinyl include S(O)CH 3 , S(O)C 2 H 5 , n-propylsulfinyl,
  • Ci-C ⁇ -alkylsulfinyl further encompass n- pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 1 ,1- dimethylpropylsulfinyl, 1 ,2-dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl, 1- ethylpropylsulfinyl, n-hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3- methylpentylsulfinyl, 4-methylpentylsulfinyl, 1 ,1-dimethylbutylsulfinyl, 1 ,2- dimethylbutylsulfinyl, 1 ,3-dimethylbutylsulfinyl, 2,2-d
  • C1-C4- alkylsulfonyl examples include SO 2 -CH 3 , SO 2 -C 2 H 5 , n-propylsulfonyl, SO 2- -CH(CHs) 2 , n- butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and SO 2 -C(CHs)3.
  • Ci-C ⁇ -alkylsulfonyl further encompass n-pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1 ,1-dimethylpropylsulfonyl, 1 ,2- dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, n- hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4- methylpentylsulfonyl, 1 ,1-dimethylbutylsulfonyl, 1 ,2-dimethylbutylsulfonyl, 1 ,3- dimethylbutylsulfonyl,
  • Ci-C4-haloalkylsulfonyl include chloromethylsulfonyl, dichloromethylsulfonyl, trichloromethylsulfonyl, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsul- fonyl, chlorofluoromethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsul- fonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2- iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2- fluoroethylsulfonyl,
  • Ci-C ⁇ -haloalkylsulfonyl further encompass 5-fluoro-1-pentylsulfonyl, 5-chloro-1-pentylsulfonyl, 5-bromo-1- pentylsulfonyl, 5-iodo-1-pentylsulfonyl, 5,5,5-trichloro-1-pentylsulfonyl, undecafluoro- pentylsulfonyl, 6-fluoro-1-hexylsulfonyl, 6-chloro-1-hexylsulfonyl, 6-bromo-1- hexylsulfonyl, 6-iodo-1-hexylsulfonyl, 6,6,6-trichloro-1-hexylsulfonyl and dodecafluoro- hexylsulfonyl.
  • chloromethylsulfonyl particularly preferred are chloromethylsulfonyl, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl and 2,2,2-trifluoroethylsulfonyl.
  • Ci-C ⁇ -alkylamino refers to a secondary amino group carrying one alkyl group as defined above, e.g. methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1 ,1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3-methylbutylamino, 2,2-dimethylpropylamino, 1-ethylpropylamino, hexylamino, 1 ,1-dimethylpropylamino, 1 ,2-dimethylpropylamino, 1-methylpentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1 ,1-dimethylbutylamino, 1 ,2-dimethylbutylamino,
  • di(Ci-C6-alkyl)amino) refers to a tertiary amino group carrying two alkyl radicals as defined above, e.g. dimethylamino, diethylamino, di-n-propylamino, diiso- propylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-
  • C2-C6-alkenyl as used herein and in the alkenyl moieties of C2-C6-alkenyloxy, C2-C6-alkenylamino, C2-C6-alkenylthio, C2-C6-alkenylsulfonyl, (C2-C6-alkenyl)carbonyl, (C2-C6-alkenyloxy)carbonyl and (C2-C6-alkenyl)carbonyloxy refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl; 1-pentenyl, 2-pentenyl
  • C2-C6-alkenyloxy refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as vinyloxy, allyloxy (propen-3-yloxy), methallyloxy, buten-4-yloxy, etc.
  • C2-C6-alkenylthio refers to a straight-chain or branched al- kenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example vinylsulfanyl, allylsulfanyl (propen-3-ylthio), methallylsufanyl, buten-4-ylsulfanyl, etc..
  • C2-C6-alkenylcarbonyl refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is bonded via the carbon atom of the carbonyl group at any bond in the alkenyl group, for example vinylcarbonyl, allylcarbonyl (propen-3-ylcarbonyl), methallylcarbonyl, buten-4- ylcarbonyl, etc.
  • C2-C6-alkenylamino refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example vinylamino, allylamino (propen-3-ylamino), methallylamino, buten-4-ylamino, etc.
  • C2-C6-alkenylsulfonyl refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfonyl (SO2) group, for example vinylsulfonyl, allylsulfonyl (propen-3-ylsulfonyl), methallylsufonyl, buten-4-ylsulfonyl, etc.
  • SO2 sulfonyl
  • C2-C6-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1-yn-1-yl, prop-2- yn-1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent-1-yn
  • C2-C6-alkynyloxy refers to a straight-chain or branched al- kynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as propargyloxy (propyn-3-yloxy), butyn-3-yloxy, and butyn-4-yloxy.
  • C2-C6-alkynylthio refers to a straight-chain or branched al- kynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, such as propargylsulfanyl (propyn-3-ylthio), butyn-3-ylsufanyl and butyn- 4-ylsulfanyl.
  • C2-C6-alkynylcarbonyl refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is bonded via the carbon atom of the carbonyl group at any bond in the alkynyl group, for example propargylcarbonyl (propyn-3-ylcarbonyl), butyn-3-ylcarbonyl, and butyn-4-ylcarbonyl.
  • C2-C6-alkynylamino refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, such as propargylamino (propyn-3-ylamino), butyn-3-amino, and butyn- 4-ylamino.
  • C2-C6-alkynylsulfonyl refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfonyl (SO2) group, such as propargylsulfonyl (propin-3-yltsulfonyl), butin-3-ylsufonyl and butin-4-ylsulfonyl.
  • SO2 sulfonyl
  • monocyclic radicals comprise cyclo- propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
  • Examples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicy- clo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
  • Cs-C ⁇ -halocycloalkyl refers to a monocyclic hydrocarbon radical having 3 to 6 carbon atoms, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • Examples are 1- and 2- fluoro- cyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3- tetrafluorocyclpropyl, 1- and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1-,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1-,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl and the like.
  • Cs-C ⁇ -cycloalkoxy refers to a monocyclic hydrocarbon radical having 3 to 6 carbon atoms which is bound via an oxygen atom. Examples include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy and cyclohexyloxy.
  • aryl refers to a C ⁇ -C-u carboaromatic group, such as phenyl, Naphthyl, anthracenyl and phenanthrenyl.
  • aryl is phenyl.
  • aryl-Ci-C4-alkyl refers to aryl as defined above which is bound via a Ci-C4-alkyl group, in particular a methyl or an ethyl group, to the remainder of the molecule. Examples are benzyl, 2-phenylethyl, naphthylmethyl and the like.
  • aryl-Ci-C4-alkoxy refers to aryl-Ci-C4-alkyl as defined above which is bound via an oxygen atom to the remainder of the molecule (aryl-Ci-C4-alkyl- O-).
  • aryl-Ci-C4-alkyl- O- One example is benzoxy.
  • aryloxy refers to aryl as defined above which is bound via an oxygen atom to the remainder of the molecule. Examples are phenoxy and naphthoxy.
  • arylcarbonyl refers to aryl as defined above which is bound via the C atom of a carbonyl group to the remainder of the molecule. Examples are benzoyl and naphthylcarbonyl.
  • Phenyl fused to phenyl is naphthyl.
  • Phenyl fused to a 5- or 6-membered non-aromatic (i.e. saturated or partially unsaturated) heterocyclic ring is for example 2,3-dihydrobenzofuranyl, benzoxolanyl, 2,3- dihydrobenzothienyl, indolinyl, chromanyl, chromenyl, benzodioxanyl and the like.
  • 2,3-dihydrobenzofuranyl benzoxolanyl
  • 2,3- dihydrobenzothienyl indolinyl
  • chromanyl chromenyl
  • heterocyclic ring refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, which may be fused to a carbocyc- lie or heterocyclic 5, 6 or 7 membered ring thus having a total number of ring members from 8 to 10, wherein in each case 1 , 2, 3 or 4, preferably 1 , 2 or 3, of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • the carbocyclic or heterocyclic fused ring is selected from C5-C7-cycloalkyl, C5-C7- cycloalkenyl, 5 to 7 membered heterocyclyl and phenyl.
  • Examples for monocyclic 5- to 6-membered heteroaromatic rings include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl and isoxa- zolyl.
  • Examples for 5- to 6-membered heteroaromatic rings being fused to a phenyl ring are quinolinyl, iso- quinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl, and benzimidazolyl.
  • Examples for 5- to 6-membered heteroaromatic rings being fused to a cycloalkenyl ring are dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydrochinolinyl, dihydroiso- chinolinyl, chromenyl, chromanyl and the like.
  • hetaryloxy refers to hetaryl as defined above which is bound via an oxygen atom to the remainder of the molecule.
  • hetarylcarbonyl refers to hetaryl as defined above which is bound via the C atom of a carbonyl group to the remainder of the molecule.
  • (saturated, partially unsaturated or aromatic) 5 or 6-membered heterocyclic ring/ heterocyclyl comprises heteroaromatic rings as defined above and nonaromatic saturated or partially unsaturated heterocyclic rings having 5 or 6 ring members and 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms as ring members.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • non-aromatic rings examples include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3- dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1 ,3- and 1 ,4- dioxanyl, thiopyranyl, dihydrothiopyrany
  • 5-, 6- or 7-membered carbocycle comprises monocyclic aromatic rings and nonaromatic saturated or partially unsaturated carbocyclic rings having 5, 6 or 7 ring members.
  • non-aromatic rings include cyclopentyl, cyclopentenyl, cyclopentadienyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cyclohep- tenyl, cycloheptadienyl and the like.
  • linear (Ci-C6)-alkandiyl refers to methylendiyl, ethane- 1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl, hexane-1 ,6-diyl.
  • (C2-C5)-alkandiyl refers to alkylene groups such as ethane- 1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl or pentane-1 ,5-diyl, where a part or all hydrogen atoms of the alkylene groups may be substituted as defined above.
  • the term also encompasses for example -0-CH 2 -, -S-CH 2 -, -NR-CH 2 -, -0-CH 2 -CH 2 -, -S-CH 2 -CH 2 -, -NR-CH 2 -CH 2 -, -CH 2 -O-CH 2 -, -CH 2 -S-CH 2T CH 2 -NR-CH 2 -, -0-CH 2 -O-, -S-CH 2 -S-, -NR-CH 2 -NR-, -0-CH 2 -CH 2 -CH 2 -, -S-CH 2 -CH 2 -CH 2 -, -NR-CH 2 -CH 2 -CH 2 -, -NR-CH 2 -CH 2 -CH 2 -, -NR-CH 2 -CH 2 -CH 2 -, -CH 2 -O-CH 2 -CH 2 -, -CH 2 -S-CH 2 -CH 2
  • R 1 is preferably selected from the group consisting of hydrogen, cyano, Ci-C ⁇ -alkyl, Ci- C ⁇ -haloalkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl, Ci-C ⁇ -alkoxycarbonyl, Cs-C ⁇ -cycloalkyl, phenyl, benzyl, phenoxycarbonyl, 5- or 6-membered hetaryl and 5- or 6-membered hetarylmethyl each of the six last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R b1 .
  • R 1 is selected from the group consisting of hydrogen, Ci-C ⁇ -alkyl, Ci- C ⁇ -haloalkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl, phenyl, benzyl, 5- or 6-membered hetaryl and 5- or 6-membered hetarylmethyl, where each of the last four mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2 radicals R b1 .
  • R 1 is selected from the group consisting of hydrogen, C-i-C ⁇ - alkyl, phenyl and benzyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2 radicals R b1 .
  • R 1 is hydrogen
  • R 1 is different from hydrogen.
  • R 1 is in this case selected from Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl, phenyl, benzyl, 5- or 6-membered hetaryl and 5- or 6-membered hetarylmethyl, where each of the last four mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2 radicals R b1 .
  • R 1 is in this case selected from Ci-C ⁇ -alkyl, phenyl and benzyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2 radicals R b1 .
  • R b1 is preferably selected from halogen, hydroxy, amino, d-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylamino, di(Ci-C6-alkyl)amino, Ci-C ⁇ -alkylsulfonyl, CrC ⁇ -alkylcarbonyl, CrC ⁇ -alkoxycarbonyl and CrC ⁇ - alkylcarbonyloxy and more preferably from halogen, CrC ⁇ -alkyl, Ci-C6-haloalkyl, Cr C ⁇ -alkoxy and Ci-C6-haloalkoxy.
  • R 2a or R 2b are preferably selected from the group consisting of hydrogen, d-d-alkyl, formyl, CN, C(S)NR a R b , d-Ce-alkylcarbonyl, Ci-d-haloalkylcarbonyl, d- C ⁇ -alkoxycarbonyl, Ci-d-alkoxy-Ci-d-alkoxycarbonyl, d-C ⁇ -alkylthiocarbonyl, ben- zoyl, 5 or 6 membered hetarylcarbonyl, each of the last two mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 R b2 . More preferably R 2a or R 2b is hydrogen. In another preferred embodiement R 2a and R 2b are selected from the group consisting of oxazolyl, thiazolyl and imidazolyl.
  • the variables R 2a and R 2b are preferably selected from hydrogen, d-C 6 -alkyl, formyl, CN, C(S)NR a R b , d-Ce-alkylcarbonyl, CrC 6 - haloalkylcarbonyl, d-C ⁇ -alkoxycarbonyl, Crd-alkoxy-d-d-alkoxycarbonyl, CrC ⁇ - alkylthiocarbonyl, phenyl, benzoyl, benzyl, benzylcarbonyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroa- toms selected from O, S and N as ring members, hetarylmethyl, hetarylcarbonyl and hetarylmethylcarbonyl, wherein each of the 8 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals R b
  • R 2a and R 2b are selected from hydrogen, CrC ⁇ -alkyl, formyl, CN, C(S)NR a R b , d-Ce-alkylcarbonyl, Ci-Ce-haloalkylcarbonyl, d-Ce-alkoxycarbonyl, CrC 4 - alkoxy-Ci-d-alkoxycarbonyl, d-C ⁇ -alkylthiocarbonyl, benzoyl, benzylcarbonyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, hetarylcarbonyl and hetarylmethylcarbonyl, wherein each of the 5 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals R b2 , and wherein the het- eroaromatic ring in hetarylcarbon
  • R 2a is selected from hydrogen, Ci-C6-alkyl, formyl, CN, C(S)NR a R b , d-Ce-alkylcarbonyl, Ci-Ce-haloalkylcarbonyl, CrC 6 - alkoxycarbonyl, Crd-alkoxy-d-d-alkoxycarbonyl, d-C ⁇ -alkylthiocarbonyl, benzoyl, benzylcarbonyl, hetarylcarbonyl and hetarylmethylcarbonyl, wherein each of the 4 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals R b2 , and wherein the heteroaromatic ring in hetarylcarbonyl and hetarylmethyl- carbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroa- toms selected from oxygen, sulfur and nitrogen as ring
  • R 2a is selected from hydrogen, Ci-C ⁇ -alkyl, CN, d-C ⁇ -alkylcarbonyl, Ci-C ⁇ - haloalkylcarbonyl, benzoyl and hetarylcarbonyl, wherein the 2 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals R b2 , and wherein the heteroaromatic ring in hetarylcarbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring members.
  • R 2a is hydrogen or Ci-C ⁇ -alkyl, and more specifically hydrogen.
  • R 2b is selected from hydrogen, Ci-C ⁇ -alkyl, formyl, CN, C(S)NR a R b , d-Ce-alkylcarbonyl, d-Ce-haloalkylcarbonyl, CrC 6 - alkoxycarbonyl, Ci-C ⁇ -alkylthiocarbonyl, benzoyl, benzylcarbonyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, hetarylcarbonyl and hetarylmethylcarbonyl, wherein each of the 5 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals R b2 , and wherein the heteroaromatic ring in hetarylcarbonyl and hetarylmethylcarbonyl is 5- or 6-membered and contains 1 , 2, 3 or
  • R 2b is selected from hydrogen, Ci-C ⁇ -alkyl, CN, Ci-C ⁇ -alkylcarbonyl, C-i-C ⁇ - haloalkylcarbonyl, benzoyl, hetarylcarbonyl, wherein the 2 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals R b2 , and wherein the heteroaromatic ring in hetarylcarbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring members; and a 5- or 6-membered saturated, partially unsaturated or aromatic hetero- cyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members which may carry any combination of 1 , 2 or 3 radicals R b2 .
  • R 2b is selected from hydrogen, Ci-C ⁇ -alkyl and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members which may carry any combination of 1 , 2 or 3 radicals R b2 .
  • R 2b is H or a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members which may carry any combination of 1 , 2 or 3 radicals R b2 .
  • R 2b is a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members which may carry any combination of 1 , 2 or 3 radicals R b2 .
  • the 5- or 6-membered heterocyclic ring R 2b is preferably non-aromatic, i.e. saturated or partially unsaturated, and more preferably partially unsaturated.
  • the 5- or 6- membered heterocyclic ring R 2b is unsubstituted.
  • the 5- or 6-membered heterocyclic ring R 2b is 5-membered and contains two heteroatoms.
  • the 5- or 6-membered heterocyclic ring R 2b is selected from oxazolinyl and thiazolinyl, more preferably oxazolinyl and thiazolinyl which are bound in the 2-position (with respect to the 1 -position of O and S, respectively, and to the 3-position of N), and specifically R 2b is thiazolinyl which is preferably bound in the 2-position.
  • R b2 is preferably selected from halogen, hydroxy, amino, d-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy, d-C ⁇ -alkylthio, d-C ⁇ -alkylamino, di(Ci-C6-alkyl)amino, Ci-C ⁇ -alkylsulfonyl, d-C ⁇ -alkylcarbonyl, d-C ⁇ -alkoxycarbonyl and d-C ⁇ - alkylcarbonyloxy and more preferably from halogen, d-C ⁇ -alkyl, d-C ⁇ -haloalkyl, Ci- C ⁇ -alkoxy and Ci-C6-haloalkoxy.
  • radicals R 1 and R 2b together form a bridging bivalent carbonyl group C(O).
  • R 2c and R 2d are preferably selected from hydrogen, for- myl, d-C ⁇ -alkyl, d-C ⁇ -alkylcarbonyl, d-C ⁇ -alkylthiocarbonyl, d-C ⁇ -alkoxycarbonyl, Ci-C ⁇ -alkoxythiocarbonyl, arylcarbonyl, hetarylcarbonyl, aryloxycarbonyl and hetary- loxycarbonyl, where the aliphatic, aromatic or heteroaromatic moieties in the 9 last- mentioned radicals may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 radicals R c2 , and where hetaryl is a 5- or 6-membered heteroaromatic ring containing 1 , 2, 3 or 4 het- eroatoms selected from O, S and N as ring members. More preferably, R 2c and R 2d are hydrogen.
  • radicals R 4a , R 4b , R 4c and R 4d are independently selected from the group consisting of hydrogen, halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, 5- or 6- membered hetaryl, 5- or 6-membered hetarylmethyl and benzyl wherein the four last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R b4 .
  • R 4a , R 4b , R 4c and R 4d are independently selected from the group consisting of hydrogen, halogen, d-C ⁇ -alkyl, d-C ⁇ -haloalkyl, phenyl and benzyl wherein the phenyl moiety in the 2 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 radicals R b4 .
  • all radicals R 4a , R 4b , R 4c and R 4d are hydrogen.
  • At least one of the radicals R 4a , R 4b , R 4c and R 4d is different from hydrogen.
  • R 4a and/or R 4c is/are preferably different from hydrogen.
  • Particular preference is given to compounds (I) wherein R 4a and/or R 4c is/are selected from the group consisting of halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, phenyl and benzyl which may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 radicals R b4 .
  • R 4b and R 4d and optionally one of R 4a and R 4c are preferably hydrogen or Ci-C ⁇ -alkyl and more preferably hydrogen.
  • radicals R 2a and R 4a together form a bridging bivalent radical.
  • bridging radicals are
  • the radicals R c , R d and R e are selected from the group consisting of hydrogen, Ci-C ⁇ -alkyl, phenyl, hydroxy, Ci-C ⁇ -alkoxy, Ci-C ⁇ -alkylamino and di-(Ci-C6-alkyl)amino.
  • R b4 is preferably selected from halogen, hydroxy, amino, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy, d-C ⁇ -alkylthio, Ci-C ⁇ -alkylamino, di(Ci-C6-alkyl)amino, Ci-C ⁇ -alkylsulfonyl, Ci-C ⁇ -alkylcarbonyl, Ci-C ⁇ -alkoxycarbonyl and C-i-C ⁇ - alkylcarbonyloxy and more preferably from halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, Ci- C ⁇ -alkoxy and d-C ⁇ -haloalkoxy.
  • R 4a , R 4b , R 4c and R 4d are hydrogen.
  • each R Z1 is independently selected from the group consisting of halogen, OH, SH, d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkoxy, Ci-Ce-haloalkoxy, d-Ce-alkylthio and Ci-C ⁇ -haloalkylthio, more preferably from halogen, Ci-C ⁇ -alkyl, Ci-C6-haloalkyl, Ci- C ⁇ -alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio and d-C ⁇ -haloalkylthio and specifically from halogen Ci-C6-alkoxy and Ci-C6-haloalkoxy.
  • n is O or 1. In an alternatively preferred embodiment, n is 2.
  • variable X in compounds of the general formula (I) is sulfur.
  • X is O.
  • X is NR 5 .
  • X is S.
  • variable Y in compounds of the general formula (I) is sulfur.
  • Y is O.
  • Y is NR 5a .
  • Y is S.
  • R 5 and R 5a are preferably selected from hydrogen, Ci-C ⁇ -alkyl, formyl, CN, C(O)NR a R b , C(S)NR a R b , C-i-Ce-alkylcarbonyl, d-Ce-haloalkylcarbonyl, d-Ce-alkoxycarbonyl, Ci-C 4 - alkoxy-Ci-d-alkoxycarbonyl, Ci-C ⁇ -alkylthiocarbonyl, benzoyl, and hetarylcarbonyl, wherein each of the 2 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals R b5 , and wherein the heteroaromatic ring in hetarylcarbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroa- toms selected from oxygen, sulfur and nitrogen as ring members. More preferably, R 5 and R 5
  • R b5 is preferably selected from halogen, hydroxy, amino, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, Ci-C ⁇ -alkoxy, Ci-C ⁇ -haloalkoxy, d-C ⁇ -alkylthio, Ci-C ⁇ -alkylamino, di(Ci-C6-alkyl)amino, Ci-C ⁇ -alkylsulfonyl, Ci-C ⁇ -alkylcarbonyl, Ci-C ⁇ -alkoxycarbonyl and C-i-C ⁇ - alkylcarbonyloxy and more preferably from halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, Ci- C ⁇ -alkoxy and d-C ⁇ -haloalkoxy.
  • T is preferably selected from -OR T1 and -0-C(O)-R 1"3 .
  • R T1 is preferably selected from hydrogen and Ci-C6-alkyl. More preferably, R T1 is hydrogen.
  • R T3 is preferably selected from Ci-C ⁇ -alkyl which may carry 1 , 2 or 3 substituents R Ta ; C3-C6-cycloalkyl which may carry 1 , 2 or 3 substituents R Tb ; phenyl which may carry 1 , 2 or 3 substituents R Tc ; naphthyl which may carry 1 , 2 or 3 substituents R Tc ; benzo-1 ,3- dioxolanyl which may carry 1 , 2 or 3 substituents R Tc ; and 5- or 6-membered hetaryl containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, which may carry 1 , 2 or 3 substituents R Td .
  • each R Ta is independently selected from the group consisting of halogen, d-d-alkoxy, d-d-haloalkoxy, d-d-alkylthio, d-d-haloalkylthio, Ci-C 4 - alkylcarbonyl, Ci-d-haloalkylcarbonyl, Ci-d-alkoxycarbonyl, C1-C4- haloalkoxycarbonyl, Ci-d-alkylcarbonyloxy, Ci-d-haloalkylcarbonyloxy, phenyl, phenyloxy, and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the 3 last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyloxy and CrC 4 - haloal
  • each R Ta is independently selected from the group consisting of Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-alkylcarbonyl, CrC 4 - alkoxycarbonyl, phenyl, phenyloxy, and 5- or 6-membered hetaryl.
  • each R Tb is independently selected from the group consisting of halogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio, CrC 4 - haloalkylthio, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, Cr C4-haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, Ci-C4-haloalkylcarbonyloxy, phenyl, phenyloxy, and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the 3 last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalky
  • each R Tc is independently selected from the group consisting of halogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio, CrC 4 - haloalkylthio, CrC ⁇ alkylcarbonyl, CrC ⁇ haloalkylcarbonyl, CrC ⁇ alkoxycarbonyl, Cr C 4 -haloalkoxycarbonyl, CrC ⁇ alkylcarbonyloxy, and CrC ⁇ haloalkylcarbonyloxy and 5- or 6-membered hetaryl, where the hetaryl ring may carry 1 , 2 or 3 substituents selected from halogen, CrC 4 -alkyl, CrC 4 -haloalkyl, CrC ⁇ alkylcarbonyloxy and CrC 4 - haloalkylcarbonyloxy.
  • each R Td is independently selected from the group consisting of halogen, CrC 4 -alkyl, CrC 4 -haloalkyl, d-C 4 -alkoxy, CrC 4 -haloalkoxy, CrC 4 -alkylthio, CrC 4 - haloalkylthio, CrC ⁇ alkylcarbonyl, CrC ⁇ haloalkylcarbonyl, CrC ⁇ alkoxycarbonyl, Cr C 4 -haloalkoxycarbonyl, d-C ⁇ alkylcarbonyloxy, CrC ⁇ haloalkylcarbonyloxy, phenyl, phenyloxy, and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the 3 last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, CrC 4 -alkyl, CrC 4 -haloalkyl, CrC ⁇ alkyl, Cr
  • each R Td is independently selected from the group consisting of halogen, CrC 4 -alkyl, CrC 4 -haloalkyl, CrC 4 -alkoxy, CrC 4 - haloalkoxy, Ci-C 4 -alkylthio, CrC 4 -haloalkylthio, CrC ⁇ alkylcarbonyl, CrC 4 - haloalkylcarbonyl, CrC ⁇ alkoxycarbonyl, CrC ⁇ haloalkoxycarbonyl, CrC 4 - alkylcarbonyloxy, CrC ⁇ haloalkylcarbonyloxy and phenyl, where the phenyl moiety may carry 1 , 2 or 3 substituents selected from halogen, CrC 4 -alkyl, CrC 4 -haloalkyl, CrC ⁇ alkylcarbonyloxy and CrC ⁇ haloalkylcarbonyloxy.
  • Z is a group of formula (I I. A) or (II. B). Preferred mean- ings of the variables in theses groups are listed above.
  • Compounds (I) wherein Z is a group of formula (I I. A) or (II. B) represent tautomers in case R 2a and R 2b are hydrogen.
  • Z is a group of formula (II. C). Preferred meanings of the variables in theses groups are listed above.
  • Compounds (I) wherein Z is a group of formula (II. C) can serve as intermediates in the preparation of compounds (I) wherein Z is a group of formula (I I. A) or (II. B).
  • T is a group -O-R T1
  • the group T can be converted into a leaving group, especially if R T1 is H, e.g. by converting it into the corresponding tosylate or halogenide.
  • Compounds (I) wherein T is a group -O-C(O)-R T3 can be reacted directly to the corresponding compound (I) wherein Z is a group (I I. A) or (II. B).
  • compounds (I) wherein Z is a group of formula (II. C) have themselves a good activity profile against harmful animal pests and can thus be used without further conversion.
  • Particularly preferred compounds (I) are those of the formulae (I.A.1), (I.A.2), (I.B.1), (I.B.2), (I.C.1 ), (I.C.2), (I.C.3) and (I.C.4) below:
  • Examples of particularly preferred compounds of the general formula I are the compounds I compiled in Tables 1 to 176 below. Moreover, the meanings mentioned for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
  • Tables 33 to 48 Compounds of the formulae (LA.1 ) or (I.B.1 ) and their mixtures, wherein the combination of X and R 1 is as defined in any of Tables 1 to 16, the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of Table A and R 2a or R 2b is -C(O)CH3 instead of hydrogen.
  • Table 119 Compounds of the formula (I.C.1), wherein Y is NH, R 1 is CH3 and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 124 Compounds of the formula (I.C.1), wherein Y is NCH3, R 1 is phenyl and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 125 Compounds of the formula (I.C.1), wherein Y is O, R 1 is benzyl and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 135 Compounds of the formula (I. C.2), wherein Y is NH, R 1 is CH3 and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 143 Compounds of the formula (I. C.2), wherein Y is NH, R 1 is benzyl and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 147 Compounds of the formula (I. C.3), wherein Y is NH, R 1 is hydrogen, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 148 Compounds of the formula (I. C.3), wherein Y is NCH3, R 1 is hydrogen, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 ) n , R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 149 Compounds of the formula (I. C.3), wherein Y is O, R 1 is CH3, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 150 Compounds of the formula (I. C.3), wherein Y is S, R 1 is CH3, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 151 Compounds of the formula (I. C.3), wherein Y is NH, R 1 is CH3, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 ) n , R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 152 Compounds of the formula (I. C.3), wherein Y is NCH3, R 1 is CH3, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 153 Compounds of the formula (I. C.3), wherein Y is O, R 1 is phenyl, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 ) n , R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 154 Compounds of the formula (I. C.3), wherein Y is O, R 1 is phenyl, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 ) n , R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 154 Compounds of the formula (I. C.3), wherein Y is O, R 1 is phenyl, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 ) n , R 4a and R 4b for
  • Table 170 Compounds of the formula (I. C.4), wherein Y is S, R 1 is phenyl, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 171 Compounds of the formula (I. C.4), wherein Y is NH, R 1 is phenyl, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 ) n , R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 172 Compounds of the formula (I. C.4), wherein Y is NCH3, R 1 is phenyl, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 173 Compounds of the formula (I. C.4), wherein Y is O, R 1 is benzyl, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 174 Compounds of the formula (I. C.4), wherein Y is S, R 1 is benzyl, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 ) n , R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 175 Compounds of the formula (I. C.4), wherein Y is NH, R 1 is benzyl, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 )n, R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • Table 176 Compounds of the formula (I. C.4), wherein Y is NCH3, R 1 is benzyl, R T3 has in each case one of the meanings given in one row of table B and the combination of (R z1 ) n , R 4a and R 4b for a compound corresponds in each case to one row of table A.
  • compounds (I) wherein Z is a group (I I. A) are named compounds (I .A)
  • compounds (I) wherein Z is a group (II. B) are named compounds (I. B)
  • compounds (I) wherein Z is a group (II. C) are named compounds (I. C).
  • the compounds of the formula (I. A) according to the invention wherein X is oxygen or sulphur and R 2a is hydrogen (referred herein as compounds I.A.a) can be prepared e.g. from the corresponding urea compounds IV and thiourea compounds III, respectively, as shown in scheme 1.
  • R 1 , R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , R Z1 , m and n have the meanings given above.
  • the thiourea compound (III) and the urea compound (IV), respectively can be cyclized by conventional means thereby obtaining the azoline compound of the formula (I.A.a). Cyclization of the compound (III) and (IV), respectively, can be achieved e.g. under acid catalysis or under dehydrating conditions e.g. by Mitsunobu's reaction (see Tetrahedron Letters 1999, 40, 3125-3128).
  • the cyclization can be carried out in the presence of a trialkyl- or tricy- cloalkylphosphine, such as trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine or tricyclohexylphosphine, a triarylphosphine, such as triphenylphosphine, or, preferably, in the presence of a phosphonium salt of the formula [P(R ⁇ ) 3 R ⁇ ] + A- wherein R ⁇ is Ci-C 4 -alkyl, cyclohexyl or phenyl; R ⁇ is CH 2 -U, where U is Ci-C4-alylcarbonyl, Ci-C4-alkoxycarbonyl or, preferably, CN; and A is an anion equivalent, for example a halide anion.
  • a particularly suited phosphorus reagent is cyanomethyltrimethylphosphonium iodide (see Tetrahedron 2001 , 57, 5451-54).
  • this variant is suitably carried out in the presence of a base, which is suitably an amine, such as triethylamine or diisopropylethylamine.
  • a base which is suitably an amine, such as triethylamine or diisopropylethylamine.
  • This variant can be carried out in analogy to the method described in US 2005/0032814.
  • the compounds of the formula (I. A) according to the invention wherein X is O or S and R 2a , R 3a , R 3b , R 3c and R 3d are hydrogen (referred herein as compounds (I.A.b)) can be prepared by the method shown in scheme 2.
  • R 1 , R 4a , R 4b , R 4c , R 4d , R Z1 , m and n have the meanings given above.
  • An amine V or a salt thereof can be converted into an azoline (I.A.b) by reaction with 2- chloroethylisothiocyanate or 2-chloroethylisocyanate (e.g. as described in Bioorg. Med. Chem. Lett. 1994, 4, 2317-22) and subsequent cyclization in the presence or absence of a base.
  • 2- chloroethylisothiocyanate or 2-chloroethylisocyanate e.g. as described in Bioorg. Med. Chem. Lett. 1994, 4, 2317-22
  • R 1 , R 4a , R 4b , R 4c , R 4d , R Z1 , m and n have the meanings given above.
  • X is O or S.
  • LG is a leaving group, e.g. a halogen atom, a tosylate or a triflate group.
  • Compounds of the formula (I.A.c) may be obtained by reacting an appropriate substituted amine (V) or a salt thereof with a 2-substituted imidazoline (Vl) in an appropriate solvent. This reaction can be carried out, for example analogous to the methods described in US 5,130,441 or EP 0389765.
  • Amines (V) are known in the art or can be prepared by methods familiar to an organic chemist, for instance by application of general methods for the synthesis of amines.
  • Suitable amine salts (V) are e.g. the acid addition salts formed by treating an amine (V) with an inorganic or organic acid.
  • Anions of useful acids are e.g. sulfate, hydrogen sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, chloride, bromide, p-toluene sulfonate, and the anions of Ci-C4-alkanoic acids such as acetate, propionate, and the like.
  • amines (V) can be prepared from suitable ketones (VII) by the methods depicted in schemes 4 and 5 below.
  • R 4a , R 4b , R 4c , R 4d , R Z1 , m and n have the meanings given above.
  • Amines (V) wherein R 1 is hydrogen (V.a) can be obtained through reductive amination using e. g. NH 4 OAc and NaCNBHs or NH2 ⁇ H/ZnOAc (see R. C. Larock, Comprehensive Organic Transformations 2 nd Ed., Wiley-VCH, 1999, p. 843-846).
  • compounds (V.a) can be prepared by reduction of the ketone and subsequent amination of the resulting alcohol (see Mitsunobu, Hughes, Organic Reactions 1992, 42, 335-656).
  • R 1 , R 4a , R 4b , R 4c , R 4d , R Z1 , m and n have the meanings given above.
  • Amines (V) wherein R 1 is different from hydrogen (V. b) can be obtained from the ketone (VII) via a two step synthesis.
  • a first step the ketone is reacted with a suitable sulfinamide such as (2-methyl-2-propane)sulfinamide in presence of a Lewis acid such as titanium tetraalkylate, e.g. titanium tetraisopropylate or titanium tetraethyl.
  • the radical R 1 is subsequently introduced via a nucleophilic addition of a metallorganic compound R 1 -Met followed by protonation and deprotection of the amino group.
  • ketones are known in the art or can be prepared by methods familiar to an organic chemist, for instance by application of general methods for the synthesis of ketones, lndanone (ketone (VII) wherein m is 1 , n is 0 and R 4a , R 4a , R 4a , and R 4a are H) and ⁇ -tetralon (ketone (VII) wherein m is 2, n is 0 and R 4a , R 4a , R 4a , and R 4a are H) are commercially available.
  • Schemes 6 and 7 below illustrate some synthetic routes towards substituted ketones (VII).
  • Epoxidation and subsequent cleavage and water elimination can be carried out by standard procedures as described, for example, in J. March, Advanced Organic Chemistry, Wiley.
  • Suitable epoxidation reagents are for example peracids, such as perfumaric acid, peracetic acid, perbenzoic acid and m-chloroperbenzoic acid.
  • Ketones (VII) wherein at least one of the radicals R 4a , R 4b , R 4c and R 4d is different from hydrogen (if R 4c and/or R 4d are different from hydrogen, they are directly neighboured to the carbonyl group in case m is 2) can be obtained from a suitable ⁇ -unsubstituted ketone (Vll.a) via alkylation or palladium-catalyzed arylation (see M. Palucki, S. L. Buchwald J. Am. Chem. Soc. 1997, 1 19, 1 1108-.11 109 or J. M. Fox, X. Huang, A. Chieffi, S. L. Buchwald J. Am. Chem. Soc. 2000, 122, 1360-1370) of the enolate species.
  • ⁇ -substituted ketones (VII) can be obtained from an intramolecular Friedel-Crafts-Acylation of a suitable aromatic acid chloride (see Y. Oshiro et al. J. Med. Chem. 1991 , 34, 2004-2013 or W. Vaccaro et al. J. Med. Chem. 1996, 39, 1704- 1719).
  • LG is a leaving group, e.g. a halide ion, such as Cl or Br, a tosylate or a triflate group.
  • a compound (I.A.b) wherein R 2a and R 2b , respectively, are hydrogen is treated with a suitable electrophile.
  • Suitable electrophiles are e.g. alkylating or acylating agents R 2a,2b .
  • _(3 (LQ
  • R Z1 , R 1 , R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , m and n are as defined above.
  • X is O or S.
  • An amine (V) or a salt thereof is converted to the corresponding iso(thio)cyanate (X) by conventional means, e.g. by reacting (V) with (thio)phosgene, as described for example in the case of thiophosgene in Houben-Weyl, E4, "Methoden der Organischen Che- mie", chapter Nc, pp. 837-842, Georg Thieme Verlag 1983. It may be advantageous to carry out the reaction in the presence of a base.
  • the iso(thio)cyanate (X) is then reacted with an aminoethanol (Xl) to form an amino(thio)carbonylaminoethane compound.
  • reaction of the aminoethanol (Xl) with iso(thio)cyanate (X) can be performed in accordance with standard methods of organic chemistry, see e.g. Biosci. Biotech. Biochem. 56 (7), 1062-65 (1992).
  • R Z1 , R 1 , R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , m and n are as defined above.
  • An amine (V) or a salt thereof can be converted to the corresponding thiourea compound (III) by reaction of the amine (V) with an isothiocyanate (XII) and subsequent saponification (see G. Liu et al. J. Org. Chem. 1999, 64, 1278-1284).
  • lsothiocyanates of formula (XII) can be prepared according to the procedures described in Coll. Czech. Chem. Commun. 1986, 51 , 1 12-117.
  • Compounds III and IV belong to the group of compounds (I. C). They can be converted into compounds (I. C) wherein T is OR T1 with R T1 being different from hydrogen by standard etherification procedures, e.g.
  • T is SR T2
  • T is SR T2
  • Compounds (III) and (IV) can also be converted into compounds (I.C) wherein T is -0-C(O)-R 1"3 or -0-C(S)-R 1"4 by esterification with the corresponding (thio)acid chloride CI-C(V)-R 1" , wherein V is O or S and R 1 is R 1"3 if V is O and R 1"4 if V is S, as outlined below in scheme 11.
  • X corresponds here to Y in the general formula (I.C).
  • R Z1 , R 1 , R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , m and n are as defined above.
  • X is O or S
  • V is O or S
  • R 1 is R 1"3 if V is O and R 1"4 if V is S.
  • the reaction is generally carried out in the presence of a base such as an amine.
  • a base such as an amine.
  • the (thio)acid chlorides are either commercially available or can be prepared from the corresponding acids or esters by chlorination e.g. with thionylchloride.
  • the corresponding acids and esters can be prepared by standard procedures.
  • R Z1 , R 1 , R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , m and n are as defined above.
  • Y is O or S
  • V is O or S
  • R 1 is R T3 if V and W are both O
  • R 1 is R T4 if V is S and W is O
  • R 1 is R T5 if V and W are both S.
  • An amine (V) or a salt thereof can be converted to the corresponding (thio)urea com- pound (I.C.b) by reaction of the amine (V) with an iso(thio)cyanate (XIII) (see G. Liu et al. J. Org. Chem. 1999, 64, 1278-1284). lsothiocyanates of formula (XIII) can be prepared according to the procedures described in Coll. Czech. Chem. Commun. 1986, 51 , 112-117.
  • R Z1 , R 1 , R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , m and n are as defined above.
  • LG is Cl, imidazolyl or pyrazolyl.
  • Compounds of formula (I. C) wherein Y is NH can also be synthesized as outlined in scheme 14 by reacting an amine (V) with the guanidine derivative (XV) and subsequent alkylation of the Nhb group:
  • LG 1 is Cl, imidazolyl or pyrazolyl.
  • LG 1 is a leaving group such as Cl, Br, a tosy- late or a triflate group.
  • an amine (V) is reacted with guanidine chloride or with imidazol or pyra- zolamidine (XV) to the guanidine (XVI) which is then alkylated to give the compound (I.C.d).
  • the alkylation can additionally take place at the NH groups of (XVI), thus providing compounds (I. C) wherein R 2c and/or R 2d and/or R 5a are a group -C(R 3c R 3d )-C(R 3a R 3b )-T.
  • the compounds of the formula (I) can be prepared by the methods described above. If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds (I) or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds (I) can advantageously be prepared from other compounds (I) by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like.
  • reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel.
  • Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or digestion.
  • the compounds of the general formula (I) may be used for controlling animal pests.
  • the present invention also provides a method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a plant, seed, soil, area, material or environment in which the pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of the formula I or a salt thereof or a composition as defined above.
  • the method of the invention serves for protecting seed and the plant which grows therefrom from animal pest attack or infestation and comprises treating the seed with a pesticidally effective amount of a compound of the formula I or an agriculturally acceptable salt thereof as defined above or with a pesticidally effective amount of an agricultural composition as defined above and below.
  • the method of the invention is not limited to the protection of the "substrate" (plant, seed, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated seed, the plant itself not having been treated.
  • animal pests are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes.
  • the invention further provides an agricultural composition for combating such animal pests, which comprises such an amount of at least one compound of the general formula (I) or at least one agriculturally useful salt thereof and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.
  • Such a composition may contain a single active compound of the formula (I) or a salt thereof or a mixture of several active compounds (I) or their salts according to the present invention.
  • the composition according to the present invention may comprise an individual isomer or mixtures of isomers as well as individual tautomers or mixtures of tautomers.
  • the compounds of the formula (I) and the pestidicidal compositions comprising them are effective agents for controlling arthropod pests and nematodes.
  • Animal pests controlled by the compounds of formula (I) include for example
  • Insects from the order of the lepidopterans for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lest
  • beetles Coldeoptera
  • Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12- punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtip
  • dipterans dipterans
  • Aedes aegypti Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicu- laris, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycor
  • thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci;
  • Hymenopterans e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta;
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor;
  • homopterans e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae,
  • Isoptera e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes flavipes, Reticulitermes lucifugus und Termes natalensis;
  • orthopterans e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melano- plus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus;
  • Arachnoidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
  • Arachnids Acarina
  • Argasidae e.g. of the families Argas
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis;
  • Siphonatera e.g. Xenopsylla cheopsis, Ceratophyllus spp ;
  • compositions and compounds of formula (I) are useful for the control of nema- todes, especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla,Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species;
  • cyst-forming nematodes Globodera rostochiensis and other Globodera species
  • Het- erodera avenae Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species
  • Seed gall nematodes Anguina species
  • Stem and foliar nematodes Aphelenchoides species
  • Sting nematodes Belonolaimus longicaudatus and other Belonolaimus species
  • Pine nematodes Bursaphelenchus xylophilus and other Bursaphelenchus species
  • Ring nematodes Criconema species, Criconemella species, Criconemoides species, Mesocriconema species
  • Stem and bulb nematodes Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species
  • AwI nematodes Dolichodorus
  • the compounds of formula (I) are used for controlling insects or arachnids, in particular insects of the orders Lepidoptera, Coleop- tera, Thysanoptera and Homoptera and arachnids of the order Acarina.
  • the compounds of the formula (I) according to the present invention are particularly useful for controlling insects of the order Thysanoptera and Homoptera.
  • the compounds of formula (I) or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pesticidally effective amount of compounds of formula (I).
  • crop refers both to growing and harvested crops.
  • the compounds of formula (I) can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
  • the formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4 th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq.
  • auxiliaries suitable for the formulation of agrochemicals such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, anti- foaming agents, anti-freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
  • solvents examples include water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (N-methyl-pyrrolidones [NMP], N-octyl-pyrrolidone [NOP]), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters.
  • solvent mixtures may also be used.
  • Suitable emulsifiers are nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).
  • dispersants examples include lignin-sulfite waste liquors and methylcellulose.
  • Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalene- sulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
  • Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, etha- nol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, x
  • anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
  • Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
  • a suitable preservative is e.g. dichlorophen.
  • Seed treatment formulations may additionally comprise binders and optionally colorants.
  • Binders can be added to improve the adhesion of the active materials on the seeds after treatment.
  • Suitable binders are block copolymers EO/PO surfactants but also polyvinylalcoholsl, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybute- nes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, poly- ethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, ty- lose and copolymers derived from these polymers.
  • colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • gelling agent examples include carrageen (Satiagel®).
  • Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
  • solid carriers examples include mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium ni- trate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium
  • the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound(s).
  • the active compound(s) are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).
  • respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.
  • the compounds of formula (I) can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusta- ble products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring.
  • the use forms depend entirely on the intended pur- poses; they are intended to ensure in each case the finest possible distribution of the active compound(s) according to the invention.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil and such concentrates are suitable for dilution with water.
  • the active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 % per weight.
  • the active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.
  • UUV ultra-low-volume process
  • Products for dilution with water for foliar applications may be applied to the seed diluted or undiluted.
  • the active compound(s) 10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolves upon dilution with water, whereby a formula- tion with 10 % (w/w) of active compound(s) is obtained.
  • Emulsions EW, EO, ES
  • 25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.
  • an emulsifier machine e.g. Ultraturrax
  • 50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active compound ⁇ ), whereby a formulation with 50% (w/w) of active compound(s) is obtained.
  • 75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s) , whereby a formulation with 75% (w/w) of active compound(s) is obtained.
  • 0.5 parts by weight of the active compound(s) is ground finely and associated with 95.5 parts by weightof carriers, whereby a formulation with 0.5% (w/w) of active compound ⁇ ) is obtained.
  • Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
  • the compounds of formula (I) are also suitable for the treatment of seeds.
  • Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having preger- minated the latter
  • a FS formulation is used for seed treatment.
  • a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • FS formulations of compounds of formula (I) for seed treatment com- prise from 0.5 to 80 wt% of the active ingredient, from 0,05 to 5 wt% of a wetter, from 0.5 to 15 wt% of a dispersing agent, from 0,1 to 5 wt% of a thickener, from 5 to 20 wt% of an anti-freeze agent, from 0,1 to 2 wt% of an anti-foam agent, from 1 to 20 wt% of a pigment and/or a dye, from 0 to 15 wt% of a sticker /adhesion agent, from 0 to 75 wt% of a filler/vehicle, and from 0,01 to 1 wt% of a preservative.
  • oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1 :10 to 10:1.
  • the compounds of formula (I) are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
  • compounds of formula (I) are preferably used in a bait composition.
  • the bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
  • Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks.
  • Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources.
  • Gels can be based on aqueous or oily matrices and can be formulated to par- ticular necessities in terms of stickyness, moisture retention or aging characteristics.
  • the bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it.
  • the attractiveness can be manipulated by using feeding stimulants or sex pheromones.
  • Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey.
  • Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant.
  • Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
  • Formulations of compounds of formula (I) as aerosols are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches.
  • Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g.
  • kerosenes having boiling ranges of approximately 50 to 250 0 C, dimethyl- formamide, N-methylpyrrolidone, dimethyl sulphoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
  • emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • the compounds of formula (I) and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
  • Methods to control infectious diseases transmitted by insects e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis
  • compounds of formula (I) and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like, lnsecticidal compositions for application to fibers, fabric, knitgoods, nonwov- ens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.
  • Suitable repellents for example are N,N-diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3- cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as ⁇ (+/-)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)- trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-i-epi-eucamalol or crude plant extracts from plants like Eucaly
  • Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
  • vinyl esters of aliphatic acids such as such as vinyl acetate and vinyl versatate
  • acrylic and methacrylic esters of alcohols such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate
  • mono- and di-ethylenically unsaturated hydrocarbons such as styrene
  • aliphatic diens such as butadiene.
  • the impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets.
  • seed treatment refers to all methods that bring seeds and the compounds of formula (I) into contact with each other
  • seed dressing to methods of seed treatment which provide the seeds with an amount of the compounds of formula (I), i.e. which generate a seed comprising the compound of formula (I).
  • the treatment can be applied to the seed at any time from the harvest of the seed to the sowing of the seed.
  • the seed can be treated immediately before, or during, the planting of the seed, for example using the "planter's box” method.
  • the treatment may also be carried out several weeks or months, for example up to 12 months, before planting the seed, for example in the form of a seed dressing treatment, without a substantially reduced efficacy being observed.
  • the treatment is applied to unsown seed.
  • the term "unsown seed” is meant to include seed at any period from the harvest of the seed to the sowing of the seed in the ground for the purpose of germination and growth of the plant.
  • a procedure is followed in the treatment in which the seed is mixed, in a suitable device, for example a mixing device for solid or solid/liquid mixing partners, with the desired amount of seed treatment formulations, either as such or after previous dilution with water, until the composition is distributed uniformly on the seed. If ap-litiste, this is followed by a drying step.
  • a suitable device for example a mixing device for solid or solid/liquid mixing partners
  • the compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.
  • An object of the present invention is therfore also to provide new methods to control parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.
  • the invention also relates to compositions containing a parasiticidally effective amount of compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.
  • the present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
  • the invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a compound of formula (I) or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
  • Compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infestations and infections in animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
  • mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer
  • fur-bearing animals
  • Compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
  • Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
  • the compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are suitable for systemic and/or non- systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
  • the compounds of formula (I) are especially useful for combating ectoparasites.
  • the compounds of formula (I) are especially useful for combating parasites of the fol- lowing orders and species, respectively: fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
  • cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis,
  • insects e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An- astrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Cul
  • Pediculus humanus capitis e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthi- rus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
  • ticks and parasitic mites ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Orni- thodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Orni- thonyssus bacoti and Dermanyssus gallinae,
  • Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
  • Bugs Heteropterida: Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus, Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,
  • Mallophagida suborders Arnblycerina and Ischnocerina
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp
  • Mallophagida suborders Arnblycerina and Ischnocerina
  • Trichinosis Trichosyringida
  • Trichinellidae Trichinella spp.
  • Trichuridae Trichuris spp.
  • Capillaria spp Trichinosis
  • Rhabditida e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,
  • Strongylida e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunosto- mum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp.
  • Cooperia spp. Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioc- tophyma renale,
  • Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi,
  • Ascaridida e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi
  • Ascaridida e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascar
  • Camallanida e.g. Dracunculus medinensis (guinea worm)
  • Spirurida e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Hab- ronema spp.,
  • Thorny headed worms e.g. Acanthocephalus spp., Macracantho- rhynchus hirudinaceus and Oncicola spp,
  • Planarians (Plathelminthes):
  • Flukes e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilhar- zia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp, Cercomeromorpha, in particular Cestoda (Tapeworms), e.g.
  • Diphyllobothrium spp. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.
  • the compounds of formula (I) and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
  • the compounds of formula (I) also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
  • Administration can be carried out both prophylactically and therapeutically.
  • Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
  • the formula (I) compounds may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules.
  • the formula (I) compounds may be administered to the animals in their drinking water.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula (I) compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
  • the formula (I) compounds may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the formula (I) compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
  • the formula (I) compounds may be formulated into an implant for subcutaneous administration.
  • the formula (I) compound may be transdermally administered to animals.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula (I) compound.
  • the formula (I) compounds may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions.
  • dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the formula (I) compound.
  • the formula (I) compounds may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
  • Suitable preparations are:
  • Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
  • Emulsions and suspensions for oral or dermal administration for oral or dermal administration; semi-solid preparations;
  • Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound- containing shaped articles.
  • compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers.
  • the solutions are filtered and filled sterile.
  • Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.
  • the active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
  • Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation.
  • examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
  • Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.
  • Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.
  • Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
  • Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being nec- essary.
  • solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, me- thylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylforma- mide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
  • alkyleneglycol alkylether e.g. dipropylenglycol monomethylether
  • ketons such as acetone, me- thylethylketone
  • aromatic hydrocarbons such as acetone, me- thylethylketone
  • vegetable and synthetic oils dimethylforma- mide, dimethylacetamide, transcutol, solketal, propylencarbonate,
  • thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
  • Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment- like consistency results.
  • the thickeners employed are the thickeners given above.
  • Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
  • pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added.
  • Suitable solvents are water, alkanols, glycols, polyethylene glycols, polypropylene gly- cols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyetha- nol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as al- kylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbon- ates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N-methyl
  • Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.
  • Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.
  • Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
  • Suitable light stabilizers are, for example, novantisolic acid.
  • Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacry- lates, natural polymers such as alginates, gelatin.
  • Emulsions can be administered orally, dermally or as injections.
  • Emulsions are either of the water-in-oil type or of the oil-in-water type.
  • Suitable hydrophobic phases are: liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length Cs-Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Cs-do fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, is
  • Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
  • Suitable emulsifiers are: non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monoo- leate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; cation-active surfactants, such as cetyltrimethylammonium chloride.
  • non-ionic surfactants e.g. polyethoxylated castor oil, polyethoxylated sorbitan monoo- leate, sorbitan monostearate, glycerol monoste
  • Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
  • Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
  • auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
  • Liquid suspending agents are all homogeneous solvents and solvent mixtures.
  • Suitable wetting agents are the emulsifiers given above.
  • Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
  • the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.
  • Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
  • Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
  • auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
  • lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
  • parasiticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the parasiticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of applica- tion, and the like.
  • compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of formula (I).
  • the compounds of formula (I) in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
  • Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 percent by weight, preferably from 0.1 to 65 percent by weight, more preferably from 1 to 50 percent by weight, most preferably from 5 to 40 percent by weight.
  • Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 percent by weight, preferably of 1 to 50 percent by weight.
  • the preparations comprise the compounds of formula (I) against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 percent by weight, very particularly preferably of 0.005 to 0.25 percent by weight.
  • compositions comprising the compounds of formula (I) are applied dermally / topically.
  • the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
  • solid formulations which release compounds of formula (I) in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
  • thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used.
  • Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose de- rivatives, polyamides and polyester which are sufficiently compatible with the compounds of formula (I).
  • a detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
  • compositions to be used according to this invention may also contain other active in- gredients, for example other pesticides, insecticides, herbicides, fungicides, other pesticides, or bactericides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides.
  • active in- gredients for example other pesticides, insecticides, herbicides, fungicides, other pesticides, or bactericides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides.
  • fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides.
  • these additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately
  • agents can be admixed with the agents used according to the invention in a weight ratio of 1 :10 to 10:1. Mixing the compounds (I) or the compositions comprising them in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action.
  • the following list of pesticides together with which the compounds (I) can be used, is intended to illustrate the possible combinations, but not to impose any limitation:
  • Juvenile hormone mimics hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;
  • Nicotinic receptor agonists/antagonists compounds acetamiprid, bensultap, cartap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nico- tine, spinosad (allosteric agonist), thiacloprid, thiocyclam, thiosultap-sodium, and AKD1022.
  • GABA gated chloride channel antagonist compounds chlordane, endosulfan, gamma-HCH (lindane); acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vaniliprole, the phenylpyrazole compound of formula F 1
  • Chloride channel activators abamectin, emamectin benzoate, milbemectin, Ie- pimectin;
  • METI I compounds fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufen- pyrad, tolfenpyrad, flufenerim, rotenone;
  • METI Il and III compounds acequinocyl, fluacyprim, hydramethylnon;
  • A.1 Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fen- butatin oxide, propargite, tetradifon;
  • Moulting disruptors cyromazine, chromafenozide, halofenozide, methoxy- fenozide, tebufenozide;
  • A.15. Fumigants methyl bromide, chloropicrin sulfuryl fluoride
  • Mite growth inhibitors clofentezine, hexythiazox, etoxazole;
  • A.18. Chitin synthesis inhibitors buprofezin, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, te- flubenzuron, triflumuron;
  • Lipid biosynthesis inhibitors spirodiclofen, spiromesifen, spirotetramat
  • A.25. Malononitrile compounds CF 3 (CH2)2C(CN)2CH2(CF2)3CF 2 H, CF3(CH2)2C(CN)2CH2(CF2) 5 CF 2 H, CF3(CH2)2C(CN)2(CH2)2C(CF3)2F, CF 3 (CH2)2C(CN)2(CH2)2(CF2)3CF 3 , CF 2 H(CF 2 )SCH 2 C(CN) 2 CH 2 (CF 2 )SCF 2 H, CF 3 (CH 2 ) Z C(CN) 2 CH 2 (CF 2 )SCFS, CF3(CF 2 ) 2 CH 2 C(CN) 2 CH 2 (CF 2 )sCF 2 H, CFSCF 2 CH 2 C(CN) 2 CH 2 (CF 2 )SCF 2 H, 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4,4,4- pentafluorobutyl)-malonodinitrile,
  • Microbial disruptors Bacillus thuringiensis subsp. Israelensi, Bacillus sphaericus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;
  • R is methyl or ethyl and Het * is 3,3-dimethylpyrrolidin-1-yl, 3-methylpiperidin-1- yl, 3,5-dimethylpiperidin-1-yl, 3-trifluormethylpiperidin-1-yl, hexahydroazepin-1-yl, 2,6- dimethylhexahydroazepin-1-yl or 2,6-dimethylmorpholin-4-yl.
  • Het * is 3,3-dimethylpyrrolidin-1-yl, 3-methylpiperidin-1- yl, 3,5-dimethylpiperidin-1-yl, 3-trifluormethylpiperidin-1-yl, hexahydroazepin-1-yl, 2,6- dimethylhexahydroazepin-1-yl or 2,6-dimethylmorpholin-4-yl.
  • Thioamides of formula r 1 and their preparation have been described in WO 98/28279.
  • Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004. Ben- clothiaz and its preparation have been described in EP-A1 454621. Methidathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Acetoprole and its preparation have been described in WO 98/28277. Metaflumizone and its preparation have been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779.
  • Pyrafluprole and its preparation have been de- scribed in JP 2002193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in US 6335357. Amidoflumet and its preparation have been described in US 6221890 and in JP 21010907. Flufenerim and its preparation have been described in WO 03/007717 and in WO 03/007718. AKD 1022 and its preparation have been described in US 6300348. Chloranthraniliprole has been de- scribed in WO 01/70671 , WO 03/015519 and WO 05/118552.
  • CF 3 (CH 2 )2C(CN)2(CH2)2(CF 2 ) 3 CF 3 , CF 2 H(CF2) 3 CH2C(CN)2CH2(CF2) 3 CF 2 H, CF 3 (CH 2 )2C(CN)2CH2(CF 2 ) 3 CF 3 , CF 3 (CF 2 )2CH2C(CN)2CH2(CF2) 3 CF 2 H, CF 3 CF 2 CH 2 C(CN) 2 CH 2 (CF 2 )SCF 2 H, 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4,4,4- pentafluorobutyl)-malonodinitrile, and CF 2 HCF 2 CF 2 CF 2 CH 2 C(CN) 2 CH 2 CH 2 CF 2 CF 3 have been described in WO 05/63694.
  • Fungicidal mixing partners are those selected from the group consisting of acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph, anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl, antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinicona- zole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole
  • the animal pest i.e. arthropodes and nematodes, the plant, soil or water in which the plant is growing can be contacted with the present compound(s) (I) or composition(s) containing them by any application method known in the art.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant).
  • animal pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formula (I).
  • the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
  • “Locus” means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
  • pesticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the compounds of formula (I) and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
  • the compounds of are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc.
  • the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
  • the compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
  • the compounds of formula (I) may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula I.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 2O g per 100 m 2 .
  • Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 % by weight, preferably from 0.1 to 45 % by weight, and more preferably from 1 to 25 % by weight of at least one repellent and / or insecticide.
  • the typical content of active ingredient is from 0.001 % by weight to 15 % by weight, desirably from 0.001 % by weight to 5 % by weight of active compound.
  • the content of active ingredient is from 0.001 to 80 % by weight, preferably from 0.01 to 50 % by weight and most preferably from 0.01 to 15 % by weight.
  • the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
  • the application rates of the mixture are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 200 g per 100 kg of seed.
  • M + molecular mass of the detected cationic species
  • Example 15 2-Acetoxy-2-methyl-propionic acid 2-[3-(1 ,2,3,4-tetrahydro-naphthalen-2-yl)thioureido]- ethyl ester (compound 15 )
  • a solution of 1-(2-hydroxyethyl)-3-(1 ,2,3,4-tetrahydronaphthalen-2-yl)-thiourea (0.4O g) and triethylamine (0.16 g) in anhydrous tetrahydrofuran (20 mL) was treated with acetic acid 1-chlorocarbonyl-i-methylethyl ester (0.26 g) and stirred overnight. Purification by column chromatography on silica gel yielded 0.46 g of the product as a colourless oil.
  • Ph phenyl
  • # is the binding site to the remainder of the molecule
  • the active compounds were formulated in 50:50 acetone : water and 100 ppm Kinetic ® surfactant.
  • Cotton plants at the cotyledon stage were infested by placing a heavily infested leaf from the main colony on top of each cotyledon. The aphids were allowed to transfer to the host plant overnight, and the leaf used to transfer the aphids was removed. The cotyledons were dipped in the test solution and allowed to dry. After 5 days, mortality counts were made.
  • the compounds 2a, 3a, 8b, 9a, 11 , 12, 18, 22, 24, 25, 26, 27, 28, 30, 31 , 32, 33, 34, 35, 36, 39, 40, 43, 44, 45, 46, 47, 48, 49, 51 and 52 at 300 ppm showed a mortality of at least 50% in comparison with untreated controls.
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ® surfactant.
  • Pepper plants in the 2 nd leaf-pair stage (variety 'California Wonder') were infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections were removed after 24 hr. The leaves of the intact plants were dipped into gradient solutions of the test compound and allowed to dry. Test plants were maintained under fluorescent light (24 hour photoperiod) at about 25 0 C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on check plants, was determined after 5 days.
  • Cowpea Aphid (aphis craccivora)
  • the active compounds were formulated in 50:50 acetone:water and 0.1 % (vol/vol) Alkamuls EL 620 surfactant.
  • Potted cowpea beans of 7-10 days of age are inoculated with aphids 24 h before treatment by clipping a leaf infested with cowpea aphid approximately 30 individuals.
  • the treated beans are sprayed with 5 ml of the test solution using air driven hand atomizer (Devillbis atomizer) at 25 psi, allowed to air dry and kept at 25-27°C and 50- 60% humidity for 3 days. After 72 h, mortality was assessed.
  • air driven hand atomizer (Devillbis atomizer)
  • the compounds 3a, 4b, 5a, 1 1 , 12, 18, 25, 26, 29, 30, 34, 35, 38, 39, 40, 43, 44, 45 and 47 at 300 ppm showed a mortality of at least 60% in comparison with untreated controls.
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
  • Selected cotton plants were grown to the cotyledon state (one plant per pot).
  • the cotyledons were dipped into the test solution to provide complete coverage of the foliage and placed in a well-vented area to dry.
  • Each pot with treated seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately 3-5 day old) were introduced.
  • the insects were colleted using an aspirator and an 0.6 cm, non-toxic Tygon® tubing (R-3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding.
  • the cups were covered with a reusable screened lid (150 micron mesh polyester screen PeCap from Tetko Inc). Test plants were maintained in the holding room at about 25 0 C and 20-40% relative humid- ity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.
  • Brown planthopper (nilaparvata lugens)
  • the active compounds were formulated as a 20:80 acetone:water solution.
  • Surfactant Alkamuls EL 620 was added at the rate of 0.1 % (vol/vol).
  • Potted rice plants of 3-4 weeks of age are sprayed with 10 ml of the test solution using air driven hand atomizer (Devillbis atomizer) at 1.7 bar.
  • the treated plants are allowed to dry for about 1 hour and covered with Mylar cages.
  • the plants are inoculated with 10 adults of the specie (5 male and 5 females) and kept at 25-27°C and 50-60% humidity for 3 days. Mortality is assed after 24, 48 and 72 hours after treatment. Dead insects are usually found in the water surface. Each treatment is replicated once.
  • the active compounds were formulated as a 10.000 ppm solution in a mixture of 35% acetone and water, which was diluted with water, if needed.
  • a Sieva lima bean leaf expanded to 7-8 cm in length is dipped in the test solution with agitation for 3 seconds and allowed to dry in a hood.
  • the leaf is then placed in a 100 x 10 mm petri dish containing a damp filter paper on the bottom and ten 2nd instar caterpillars.
  • observations are made of mortality, reduced feeding, or any interference with normal molting.
  • the active compounds were formulated in DMSO : water (1 : 3). Bean leaf disks were placed into microtiterplates filled with 0.8% agar-agar and 2.5 ppm OPUSTM. The leaf disks were sprayed with 2.5 ⁇ l of the test solution and 5 to 8 adult aphids were placed into the microtiterplates which were then closed and kept at 22-24°C and 35 - 45% un- der fluorescent light for 6 days. Mortality was assessed on the basis of vital, reproduced aphids. Tests were replicated 2 times.
  • the compounds 8a, 9a, 9b, 18, 33, 39, 45, 47, 49 and 53 at a concentration of the test solution of 2500 mg/L showed a mortality of at least 50%.
  • the compounds 4a, 5a, 25 and 40, at a concentration of the test solution of 2500 mg/L showed a mortality of at least 50%.
  • the active compounds were formulated in 1 :3 Dimethylsulfoxide / water. 50 to 80 eggs were placed into microtiterplates filled with 0.5% agar-agar and 14 % diet in water. The eggs were sprayed with 5 ⁇ l of the test solution, the plates were sealed with pierced foils and kept at 27-29 0 C and 75-85% humidity under fluorescent light for 6 days. Mortality was assessed on the basis of the agility of the hatched larvae. Tests were replicated 2 times.

Abstract

The present invention relates to the use of aminoazoline and urea derivatives for com- bating animal pests. The invention also relates to a method for controlling animal pests by using these compounds, to seed and to an agricultural and veterinary composition comprising said compounds and to specific azoline and urea derivatives.

Description

Aminoazoline and urea derivatives for combating animal pests
The present invention relates to the use of aminoazoline and urea derivatives for combating animal pests. The invention also relates to a method for controlling animal pests by using these compounds, to seed and to an agricultural and veterinary composition comprising said compounds and to specific azoline and urea derivatives.
Animal pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating insects, arachnids and nematodes. It is therefore an object of the present invention to provide compounds having a good pesticidal activity and showing a broad activity spectrum against a large number of different animal pests, especially against difficult to control insects, arachnids and nematodes.
2-(lndan-2-ylamino)-oxazoline compounds and 2-(1 ,2,3,4-tetrahydronapht-2-ylamino)- oxazoline, -thiazoline and -imidazoline compounds are described in EP-A-0251453 as having useful 0C2-adrenergic properties and thus being useful in the treatment of hyper- or hypoglycaemia. A pesticidal activity of these compounds is not mentioned.
WO 2007/020377 describes the use of 2-(indan-1-ylamino)-thiazoline compounds and 2-(1 ,2,3,4-tetrahydronapht-1-ylamino)-thiazoline compounds for controlling insects, acarines, nematodes or molluscs.
It is therefore an object of the present invention to provide compounds that have a good pesticidal activity, in particular insecticidal activity, and show a broad activity spectrum against a large number of different animal pests, especially against difficult to control insects.
It has been found that these objectives can be achieved by compounds of the formula I below.
Therefore, in a first aspect, the invention relates to the use of compounds of formula (I) or of a salt thereof for combating animal pests
Figure imgf000003_0001
(I) wherein
Z is a group of the formulae (I I. A), (II. B) or (II. C)
Figure imgf000003_0002
(II.A) (II. B) (M C) n is 0, 1 , 2, 3 or 4;
m is 1 or 2;
# is the binding site to the remainder of the molecule;
X is S, O or NR5;
Y is S, O or NR5a;
T is -ORT1, -SRT2, -O-C(O)-RT3, -O-C(S)-RT4 or -S-C(S)-R15;
RT1, RT2, RT3, RT4 and RT5 are selected from hydrogen,
Ci-Cβ-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, where the three last-mentioned radicals may carry 1 , 2 or 3 substituents RTa;
C3-C6-cycloalkyl which may carry 1 , 2 or 3 substituents RTb;
phenyl which may carry 1 , 2 or 3 substituents RTc; where the phenyl ring may also be fused to another phenyl ring or to a 5- or 6-membered saturated, partially unsaturated or aromatic 5- or 6-membered heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N and optionally 1 or 2 carbonyl groups as ring members, where the fused ring system may carry 1 , 2 or 3 substituents RTc; saturated, partially unsaturated or aromatic 5- or 6-membered heterocyclyl containing 1 , 2 or 3 heteroatoms selected from O, S and N and optionally 1 or 2 car- bonyl groups as ring members, which may carry 1 , 2 or 3 substituents RTd; or
RT3, RT4 and RT5 are NRT31RT32, where RT31 and RT32, independently of each other, are selected from hydrogen, C-i-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the 3 last-mentioned groups may carry 1 , 2 or 3 substituents RTa, Cs-Cβ-cycloalkyl, which may carry 1 , 2 or 3 substituents RTb; aryl and aryl-Ci-C4-alkyl, where the aryl moiety in the 2 last-mentioned groups may carry 1 , 2 or 3 substituents RTc; or
RT31 and RT32 together with the nitrogen atom to which they are bound form a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or aromatic bered heterocyclic containing 1 , 2 or 3 heteroatoms selected from O, S and N and optionally 1 or 2 carbonyl groups as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents RTd;
R1 is selected from the group consisting of hydrogen, cyano, C-i-Cβ-alkyl, Ci-Cβ- haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ- alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynylcarbonyl;
C3-C6-cycloalkyl, phenyl or benzyl, phenoxycarbonyl, 5- or 6-membered hetaryl and 5- or 6-membered hetarylmethyl each of the six last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb1;
R2a, R2b are selected from the group consisting of hydrogen, formyl, CN, d-Cε-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C-i-Cβ-alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6- alkynylcarbonyl, C-i-Cβ-alkoxycarbonyl, (C-i-Cβ-alkyOthiocarbonyl, (Ci-Cβ- alkoxy)thiocarbonyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals Ra2,
C(O)NRaRb, C(S)NRaRb, (SO2)NRaRb,
phenyl, benzoyl, phenoxycarbonyl, benzyl, benzylcarbonyl, benzyloxycarbonyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, 5- or 6-membered hetarylmethyl, 5- or 6-membered hetarylcarbonyl, 5- or 6- membered hetarylmethylcarbonyl, wherein each of the 10 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb2, and wherein the 5- or 6-membered heteroaromatic ring in hetarylmethyl, hetarylcarbonyl and hetarylmethylcarbonyl contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, and wherein the 5- or 6- membered heterocyclic ring contains 1 , 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring members; or R1 together with R2a may be Cs-Cs-alkandiyl which may carry 1 , 2, 3, 4 or 5 radicals R21 and where one or two methylene groups of the Cs-Cs-alkandiyl radical may be replaced by 1 or 2 non-adjacent heteroatoms or heteroatom-containing groups selected from O, S and NR22;
R1 together with R2b may also be a bridging carbonyl group C(O);
R2c and R2d, independently of each other, are selected from hydrogen, formyl, C-i-Cβ- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, aryl, aryl-Ci-C4-alkyl, hetaryl, hetaryl-Ci-C4- alkyl, C-i-Cβ-alkylcarbonyl, C-i-Cβ-alkylthiocarbonyl, C2-C6-alkenylcarbonyl, C2-C6- alkynylcarbonyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ-alkoxythiocarbonyl, arylcarbonyl, hetarylcarbonyl, aryloxycarbonyl and hetaryloxycarbonyl, where the aliphatic, aromatic or heteroaromatic moieties in the 17 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 radicals Rc2, and where hetaryl is a 5- or 6-membered heteroaromatic ring containing 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members;
R3a, R3b, R3c, R3d, independently of each other, are selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, d-Cβ-haloalkyl,
Ci-Cβ-alkyl, Ci-Cβ-alkylamino, di-(Ci-C6-alkyl)amino, d-Cβ-alkoxy, wherein the carbon atoms in the last 4 mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals Ra3,
C3-C6-cycloalkyl, phenyl or benzyl, each of the last three mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb3;
R4a, R4b, independently of each other, are selected from the group consisting of hydrogen, halogen, C-i-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C-i-Cβ-haloalkyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals
Ra4,
phenyl, benzyl, 5 or 6 membered hetaryl and 5 or 6 membered hetarylmethyl, each of the four last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb4, and wherein the 5 or 6 membered heteroaromatic ring in hetarylmethyl and hetaryl contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members; or
R4a together with R4b may also be =0, =NRC or =CRdRe; or
R4a together with R4b may also be C2-Cs-alkandiyl which may carry 1 , 2, 3, 4, 5 or 6 substituents R41 and where one or two methylene groups of the C2-Cs-alkandiyl radical may be replaced by 1 or 2 non-adjacent heteroatoms or heteroatom- containing groups selected from O, S and NR42; or
R2a together with R4a may form a bridging bivalent radical selected from the group con- sisting of C(O)-C(R24a)(R24b), C(S)-C(R24a)(R24b), CH2-C(R24a)(R24b), S(O)2-
C(R24a)(R24b), S(O)-C(R24a)(R24b), C(O)-O, C(S)-O, S(O)2-O, S(O)-O, C(O)-NH, C(S)-NH, S(O)2-NH, S(O)-NH;
R4c, R4d are independently defined like R4a and R4b;
R5, R5a, independently of each other, are selected from the group consisting of hydrogen, formyl, CN, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Cβ-alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynylcarbonyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ- alkylthiocarbonyl, wherein the carbon atoms in the aliphatic radicals of the afore- mentioned groups may carry any combination of 1 , 2 or 3 radicals Ra5,
C(0)NRaRb, (SO2)NRaRb, C(S)NRaRb
phenyl, benzyl, phenoxycarbonyl, 5 or 6 membered hetarylmethyl, 5 or 6 mem- bered hetarylcarbonyl and benzoyl each of the last six mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb5, and wherein the 5 or 6 membered heteroaromatic ring in hetarylmethyl and hetarylcarbonyl contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members;
each RZ1 is independently selected from the group consisting of halogen, OH, SH, SO3H, COOH, cyano, nitro, d-Ce-alkyl, d-Ce-alkoxy, d-Ce-alkylthio, C2-C6- alkenyl, C2-C6-alkenyloxy, C2-C6-alkenylthio, C2-C6-alkynyl, C2-C6-alkynyloxy, C2- Cβ-alkynylthio, Ci-Cβ-alkylsulfonyl, Ci-Cβ-alkylsulfoxyl, C2-C6-alkenylsulfonyl, C2- Ce-alkynylsulfonyl, a radical NRaRb, formyl, d-Ce-alkylcarbonyl, C2-C6- alkenylcarbonyl, d-Cβ-alkynylcarbonyl, Ci-C6-alkoxycarbonyl, C2-Cβ- alkenyloxycarbonyl, d-Cβ-alkynyloxycarbonyl, formyloxy, d-Cβ-alkylcarbonyloxy, d-Cβ-alkenylcarbonyloxy, d-Cβ-alkynylcarbonyloxy, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 ,2 or 3 radicals Raz,
C(O)NRaRb, (SO2)NRaRb, and radicals of the formula L-Cy, wherein
L is a single bond, oxygen, sulfur or Ci-C6-alkandiyl, wherein one carbon might be replaced by oxygen, Cy is selected from the group consisting of C3-Ci2-cycloalkyl, which is unsubstituted or substituted with any combination of 1 , 2, 3, 4 or 5 radicals Rbz, phenyl, naphthyl and mono- or bicyclic 5- to 10-membered heterocyclyl, which contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring mem- bers, wherein Cy is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rbz;
and wherein two radicals RZ1 that are bound to adjacent carbon atoms may form together with said carbon atoms a fused benzene ring, a fused saturated or par- tially unsaturated 5, 6, or 7 membered carbocycle or a fused 5, 6, or 7 membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals Rbz;
Ra, Rb are independently of each other selected from the group consisting of hydrogen, Ci-Cβ-alkyl, phenyl, benzyl, 5 or 6 membered hetaryl, C2-C6-alkenyl, or C2-C6- alkynyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals Raw;
Rc has one of the meanings given for Ra and Rb or is selected from the group consisting of Ci-Cβ-alkoxy, OH, NH2, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, arylamino, N-(Ci-C6-alkyl)-N-arylamino and diarylamino, wherein aryl is phenyl which may be unsubstituted or may carry 1 , 2 or 3 substituents Rbc;
Rd, Re have one of the meanings given for Ra and Rb or are independently of each other selected from d-Cβ-alkoxy or di(Ci-C6-alkyl)amino.
Ra2, Ra3, Ra4, Ra5, Raw and Raz are independently of each other selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C3-C6- cycloalkyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy,
Ci-Cβ-alkylcarbonyl, Ci-Cβ-alkoxycarbonyl, d-Cβ-alkylthio, d-Cβ-haloalkylthio, Ci-Cβ-alkylsulfonyl and Ci-Cβ-haloalkylsulfonyl;
Rb1, Rb2, Rb3, Rb4, Rb5, Rbc, Rbz and Rc2 are independently of each other selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C-i-Ce-alkyl, Ci-C6-haloalkyl, C3-C6-cycloalkyl, d-Ce-alkoxy, C2-C6- alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkoxy, Ci-C6-alkylthio, C1-C6- alkylamino, di(Ci-C6-alkyl)amino, Ci-Cβ-alkylsulfonyl, d-Cβ-alkylsulfoxyl, formyl, Ci-Cβ-alkylcarbonyl, Ci-C6-alkoxycarbonyl, formyloxy, and C-i-Cβ- alkylcarbonyloxy; R21, R24a, R24b and R41 have independently one of the meanings given for Rb1 or two radicals R21 bound to the same carbon atom may together with this carbon atom form a carbonyl group or two radicals R41 bound to the same carbon atom may together with this carbon atom form a carbonyl group;
R22, R42 independently are hydrogen, d-Cε-alkyl, C2-C6-alkenyl, d-Cβ-alkynyl, where the 3 last-mentioned groups may carry 1 , 2 or 3 substituents Ra42, C3-C6- cycloalkyl, which may carry 1 , 2 or 3 substituents Rb42; aryl and aryl-Ci-C4-alkyl, where aryl moiety in the 2 last-mentioned groups may carry 1 , 2 or 3 substituents Rc42;
each RTa is independently selected from the group consisting of halogen, C3-C6- cycloalkyl, Cs-Cβ-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, C1-C4- alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, C1-C4- haloalkylcarbonyloxy, phenyl, phenyloxy, phenylthio and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the four last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyloxy and Ci-C4-haloalkylcarbonyloxy;
each RTb is independently selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cβ-cycloalkyl, Cs-Cβ-halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Cs-Cβ-cycloalkoxy, C1-C4- alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, C1-C4- haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, Ci-C4-haloalkylcarbonyloxy, phenyl, phenyloxy, phenylthio and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the four last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkylcarbonyloxy and Ci-C4-haloalkylcarbonyloxy;
each RTc is independently selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cβ-cycloalkyl, Cs-Cβ-halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl, C1-C4- haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl, C1-C4- alkylcarbonyloxy, d^-haloalkylcarbonyloxy, phenyl, phenyloxy, phenylthio and
5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the four last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyloxy and C1-C4- haloalkylcarbonyloxy;
each RTd is independently selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cβ-cycloalkyl, Cs-Cβ-halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl, C1-C4- haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl, C1-C4- alkylcarbonyloxy,
Figure imgf000009_0001
phenyl, phenyloxy, phenylthio and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the four last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyloxy and C1-C4- haloalkylcarbonyloxy;
Ra42 is independently defined like RTa;
Rb42 is independently defined like RTb; and
Rc42 is independently defined like RTc.
Another object of the present invention is an agricultural composition containing at least one compound of the formula (I) as defined above and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
Another object of the present invention is a veterinary composition containing at least one compound of the formula (I) as defined above and/or a veterinarily acceptable salt thereof and at least one veterinarily acceptable liquid or solid carrier.
The present invention also provides a method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a plant, seed, soil, area, material or environment in which the pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of the formula I or a salt thereof or a composition as defined above.
The invention further related to a method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally effective amount of a compound of the formula (I) or a veterinally acceptable salt thereof as defined above. Bringing the animal in contact with the compound (I), its salt or the veterinary composition of the invention means applying or ad- ministering it to the animal.
A further object of the present invention is seed, comprising at least one compound of formula (I) and/or an agriculturally acceptable salt thereof.
Object of the invention are furthermore azoline compounds of the general formula I as defined above and salts thereof, except for compounds wherein n is 0, or n is 1 or 2 with RZ1 being d-Cβ-alkyl, d-Cβ-alkoxy or halogen, Z is a group of formula (I I. A) or (II. B) and R2a, R2b, R4a, R4b, R4c and R4d are all hydrogen.
Object of the invention are also azoline compounds of the general formula I as defined above and salts thereof, except for compounds wherein n is 0 or n is 1 or 2 with RZ1 being d-Cβ-alkyl, d-Cβ-alkoxy, halogen, phenyl or naphthyl, and simultaneously Z is a group of formula (II. A) or (II. B), R2a, R2b, R3a, R3b, R3c and R3d are all hydrogen and one of R4a and R4b is hydrogen and the other is hydrogen or d-Cβ-alkyl and one of R4c and R4d is hydrogen and the other is hydrogen or Ci-C6-alkyl.
In one embodiment, the present invention relates to azoline compounds of the general formula I as defined above and salts thereof, except compounds wherein R2a and R2b are both hydrogen.
In another embodiment the present invention also relates to azoline compounds of the general formula I as defined above and salts thereof, except compounds wherein R4a, R4b, R4c and R4d are all hydrogen.
In yet another embodiment the present invention relates to azoline compounds of the general formula I as defined above and salts thereof, except compounds wherein n is 0 or n is 1 or 2 and RZ1 is d-Cβ-alkyl, d-Cβ-alkoxy or halogen.
In the compounds of formula (I), the carbon atom which carries the radical R1 creates a center of chirality. If there is no mirror plane σ through this atom, which is for example the case when m is 2 and/or at least one of R4a, R4b, R4c and R4d is not hydrogen, the saturated cycle however not being symmetrically substituted, and/or n is not 0, the phenyl ring however not being symmetrically substituted, the compound (I) can be present in the form of different enantiomers or diastereomers, depending on the substitu- ents. In case Z is of the formula (II. B), the compound (I) may also exist as a cis- or trans-isomer with respect to the N=C axis. The present invention relates to every possible stereoisomer of the compounds of general formula (I), i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
Salts of the compounds of the formula (I) are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula (I) with a suitable base.
Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suit- able cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4 +) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci- C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammo- nium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl- ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl- triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4- alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and bu- tyrate. They can be formed by reacting a compound of formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
By the term "veterinarily acceptable salts" is meant salts of those cations or anions which are known and accepted in the art for the formation of salts for veterinary use. Suitable acid addition salts, e.g. formed by compounds of formula ()l containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hy- drochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
The term halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
Examples of other meanings are:
The term "Ci-Cβ-alkyl" as used herein and in the alkyl moieties of d-Cβ-alkoxy, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, C-i-Cβ-alkylthio, Ci-Cβ-alkylsulfonyl, Ci-Cβ-alkylsulfoxyl, d-Cβ-alkylcarbonyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ-alkylthiocarbonyl, Ci-Cβ-alkoxythiocarbonyl, and Ci-Cβ-alkylcarbonyloxy refer to a saturated straight- chain or branched hydrocarbon group having 1 to 6 carbon atoms, especially 1 to 4 carbon groups (= Ci-C4-alkyl). Examples for Ci-C4-alkyl are methyl, ethyl, propyl, 1- methylethyl (isopropyl), butyl, 1-methylpropyl (sec-butyl, 2-butyl), 2-methylpropyl (iso- butyl), and 1 ,1-dimethylethyl (tert-butyl). Examples for Ci-Cβ-alkyl further encompass pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl- 2-methylpropyl.
The term "Ci-Cβ-haloalkyl" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C4-haloalkyl, such as chloromethyl, bromomethyl, di- chloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoro- ethyl and the like.
The term "Ci-Cβ-alkoxy" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (=Ci-C4-alkoxy) (as mentioned above) which is attached via an oxygen atom. Examples for C1-C4- alkoxy include methoxy, ethoxy, OCH2-C2H5 (propoxy), OCH(CH3)2 (isopropoxy), n- butoxy, OCH(CH3)C2H5 (sec-butoxy), OCH2CH(CHs)2 (isobutoxy) and OC(CHs)3 (tert- butoxy). Examples for Ci-Cβ-alkoxy further encompass n-pentoxy, 1-methylbutoxy, 2- methylbutoxy, 3-methylbutoxy, 1 ,1-dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2- dimethyl-propoxy, 1 -ethyl propoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3- methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3- dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1- ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1-ethyl-1- methylpropoxy, 1-ethyl-2-methylpropoxy and the like.
The term "Ci-Cβ-haloalkoxy" as used herein refers to a Ci-C6-alkoxy group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Preferred are Ci-C4-haloalkoxy groups, i.e. C1-C4- alkoxy groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2- chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2- trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2,2- difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3- dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3- trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2- fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy, 4- fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy, nonafluorobutoxy. Examples for Ci-Cβ- haloalkoxy further encompass 5-fluoro-1-pentoxy, 5-chloro-1-pentoxy, 5-bromo-1- pentoxy, 5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1- hexoxy, 6-chloro-1-hexoxy, 6-bromo-1-hexoxy, 6-iodo-1-hexoxy, 6,6,6-trichloro-1- hexoxy and dodecafluorohexoxy. Particularly preferred are chloromethoxy, fluorometh- oxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2- trifluoroethoxy.
The term "Ci-Ce-alkoxy-Ci-Cβ-alkyl" as used herein refers to d-Cε-alkyl wherein 1 carbon atom carries a Ci-Cβ-alkoxy radical as mentioned above. Examples are CH2OCH3, CH2-OC2H5, n-propoxymethyl, CH2-OCH(CH3)2, n-butoxymethyl, (1-methylpropoxy)- methyl, (2-methylpropoxy)methyl, CH2-OC(CH3)S, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2- (n-propoxy)-ethyl, 2-(1-methylethoxy)-ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)- ethyl, 2-(2-methylpropoxy)-ethyl, 2-(1 ,1-dimethylethoxy)-ethyl, 2-(methoxy)-propyl, 2- (ethoxy)-propyl, 2-(n-propoxy)-propyl, 2-(1-methylethoxy)-propyl, 2-(n-butoxy)-propyl, 2-(1-methylpropoxy)-propyl, 2-(2-methylpropoxy)-propyl, 2-(1 ,1-dimethylethoxy)-propyl, 3-(methoxy)-propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)-propyl, 3-(1-methylethoxy)-propyl, 3-(n-butoxy)-propyl, 3-(1-methylpropoxy)-propyl, 3-(2-methylpropoxy)-propyl, 3-(1 ,1- dimethylethoxy)-propyl, 2-(methoxy)-butyl, 2-(ethoxy)-butyl, 2-(n-propoxy)-butyl, 2-(1- methylethoxy)-butyl, 2-(n-butoxy)-butyl, 2-(1-methylpropoxy)-butyl, 2-(2- methylpropoxy)-butyl, 2-(1 ,1-dimethylethoxy)-butyl, 3-(methoxy)-butyl, 3-(ethoxy)-butyl, 3-(n-propoxy)-butyl, 3-(1-methylethoxy)-butyl, 3-(n-butoxy)-butyl, 3-(1-methylpropoxy)- butyl, 3-(2-methylpropoxy)-butyl, 3-(1 ,1-dimethylethoxy)-butyl, 4-(methoxy)-butyl, 4- (ethoxy)-butyl, 4-(n-propoxy)-butyl, 4-(1-methylethoxy)-butyl, 4-(n-butoxy)-butyl, 4-(1- methylpropoxy)-butyl, 4-(2-methylpropoxy)-butyl, 4-(1 ,1-dimethylethoxy)-butyl and the like.
The term "(Ci-C6-alkyl)carbonyl" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci- C4-alkylcarbonyl) (as mentioned above) bonded via the carbon atom of the carbonyl group at any bond in the alkyl group. Examples for Ci-C4-alkylcarbonyl include C(O)CH3, C(O)C2H5, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1- methylpropylcarbonyl, 2-methylpropylcarbonyl and 1 ,1-dimethylethylcarbonyl. Examples for Ci-Cβ-alkylcarbonyl further encompass n-pentylcarbonyl, 1- methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1 ,1- dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl, 2,2-dimethylpropylcarbonyl, 1- ethylpropylcarbonyl, n-hexylcarbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1 ,1-dimethylbutylcarbonyl, 1 ,2- dimethylbutylcarbonyl, 1 ,3-dimethylbutylcarbonyl, 2,2-dimethylbutylcarbonyl, 2,3- dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2- ethylbutylcarbonyl, 1 ,1 ,2-trimethylpropylcarbonyl, 1 ,2,2-trimethylpropylcarbonyl, 1- ethyl-1-methylpropylcarbonyl or i-ethyl-2-methylpropylcarbonyl and the like.
The term "(Ci-C6-haloalkyl)carbonyl" as used herein refers to a straight-chain or branched saturated haloalkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-haloalkylcarbonyl) (as mentioned above) bonded via the carbon atom of the carbonyl group at any bond in the haloalkyl group. Examples include chloromethylcarbonyl, bromomethylcarbonyl, dichloromethylcarbonyl, trichloromethyl- carbonyl, fluoromethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl, chloro- fluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 1- chloroethylcarbonyl, 1-bromoethylcarbonyl, 1-fluoroethylcarbonyl, 2- fluoroethylcarbonyl, 2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, 2-chloro-2- fluoroethylcarbonyl, 2-chloro-2,2-difluoroethylcarbonyl, 2,2-dichloro-2- fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, pentafluoroethylcarbonyl and the like.
The term "(Ci-C6-alkoxy)carbonyl" as used herein refers to a straight-chain or branched alkoxy group (as mentioned above) having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkoxycarbonyl) attached via the carbon atom of the carbonyl group (R-O-C(O)-; R = alkyl). Examples for Ci-C4-alkoxycarbonyl include C(O)OCH3, C(O)OC2H5, C(O)O-CH2-C2H5, C(O)OCH(CHs)2, n-butoxycarbonyl, C(O)OCH(CH3)- C2H5, C(O) OCH2CH(CHs)2 and C(O) OC(CH3)s. Examples for d-Ce-alkoxycarbonyl further encompass n-pentoxycarbonyl, 1-methylbutoxycarbonyl, 2- methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1- ethylpropoxycarbonyl, n-hexoxycarbonyl, 1 ,1-dimethylpropoxycarbonyl, 1 ,2- dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3- methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1 ,1-dimethylbutoxycarbonyl, 1 ,2- dimethylbutoxycarbonyl, 1 ,3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2,3- dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2- ethylbutoxycarbonyl, 1 ,1 ,2-trimethylpropoxycarbonyl, 1 ,2,2-trimethylpropoxycarbonyl, 1-ethyl-1-methylpropoxycarbonyl or 1-ethyl-2-methylpropoxycarbonyl.
The term "(Ci-C6-haloalkoxy)carbonyl" as used herein refers to a straight-chain or branched saturated haloalkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-haloalkoxycarbonyl) (as mentioned above) bonded via the car- bon atom of the carbonyl group (R-O-C(O)-; R = haloalkyl). Examples include chloro- methoxycarbonyl, bromomethoxycarbonyl, dichloromethoxycarbonyl, trichloromethoxy- carbonyl, fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, chlorofluoromethoxycarbonyl, dichlorofluoromethoxycarbonyl, chlorodifluoromethoxy- carbonyl, 1-chloroethoxycarbonyl, 1-bromoethoxycarbonyl, 1-fluoroethoxycarbonyl, 2- fluoroethoxycarbonyl, 2,2-difluoroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 2- chloro-2-fluoroethoxycarbonyl, 2-chloro-2,2-difluoroethoxycarbonyl, 2,2-dichloro-2- fluoroethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, pentafluoroethoxycarbonyl and the like.
The term
Figure imgf000015_0001
as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylcarbonyloxy) (as mentioned above) bonded via the carbon atom of the carbonyloxy group at any bond in the alkyl group. Examples for C1-C4- alkylcarbonyloxy include O-CO-CH3, O-CO-C2H5, n-propylcarbonyloxy, 1 -methylethylcarbonyloxy, n-butylcarbonyloxy, 1 -methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy and 1 ,1-dimethylethylcarbonyloxy. Examples for Ci-Cβ- alkylcarbonyloxy further encompass n-pentylcarbonyloxy, 1-methylbutylcarbonyloxy, 2- methylbutylcarbonyloxy, 3-methylbutylcarbonyloxy, 1 ,1-dimethylpropylcarbonyloxy or 1 ,2-dimethylpropylcarbonyloxy.
The term "(Ci-C6-haloalkyl)carbonyloxy" as used herein refers to a straight-chain or branched saturated haloalkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-haloalkylcarbonyloxy) (as mentioned above) bonded via the carbon atom of the carbonyloxy group at any bond in the haloalkyl group (R-C(O)-O-; R = haloalkyl). Examples for Ci-C4-haloalkylcarbonyloxy include chloromethylcarbonyloxy, bromomethylcarbonyloxy, dichloromethylcarbonyloxy, trichloromethylcarbonyloxy, fluoromethylcarbonyloxy, difluoromethylcarbonyloxy, trifluoromethylcarbonyloxy, chlorofluoromethylcarbonyloxy, dichlorofluoromethylcarbonyoxyl, chlorodifluoromethyl- carbonyloxy, 1-chloroethylcarbonyloxy, 1-bromoethylcarbonyloxy, 1- fluoroethylcarbonyloxy, 2-fluoroethylcarbonyloxy, 2,2-difluoroethylcarbonyloxy, 2,2,2- trifluoroethylcarbonyloxy, 2-chloro-2-fluoroethylcarbonyloxy, 2-chloro-2,2- difluoroethylcarbonyloxy, 2,2-dichloro-2-fluoroethylcarbonyloxy, 2,2,2- trichloroethylcarbonyloxy, pentafluoroethylcarbonyloxy and the like
The term "d-Cε-alkylthio "(Ci-Cβ-alkylsulfanyl: C-i-Cε-alkyl-S-)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, prefera- bly 1 to 4 carbon atoms (= Ci-C4-alkylthio) (as mentioned above) which is attached via a sulfur atom. Examples for Ci-C4-alkylthio include methylthio, ethylthio, propylthio, 1- methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1 ,1- dimethylethylthio. Examples for d-Cε-alkylthio further encompass n-pentylthio, 1- methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1- ethylpropylthio, n-hexylthio, 1 ,1-dimethylpropylthio, 1 ,2-dimethylpropylthio, 1- methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1 ,1- dimethylbutylthio, 1 ,2-dimethylbutylthio, 1 ,3-dimethylbutythio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutlthio, 2-ethylbutylthio, 1 ,1 ,2- trimethylpropylthio, 1 ,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1 -ethyl-2- methylpropylthio.
The term "Ci-Cβ-haloalkylthio" as used herein refers to a d-Cε-alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Preferred are Ci-C4-haloalkylthio groups, i.e. C1-C4- alkylthio groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoro- methylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2- fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2- difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2- difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethyl- thio, 2-fluoropropylthio, 3-fluoropropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2,3-dichloropropylthio, 2-bromopropylthio, 3- bromopropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3- pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1- (chloromethyl)-2-chloroethylthio, 1 -(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio, nonafluorobutylthio. Examples for Ci-Cβ- haloalkylthio further encompass 5-fluoro-1-pentylthio, 5-chloro-1-pentylthio, 5-bromo-1- pentylthio, 5-iodo-1-pentylthio, 5,5,5-trichloro-1-pentylthio, undecafluoropentylthio, 6- fluoro-1-hexylthio, 6-chloro-1-hexylthio, 6-bromo-1-hexylthio, 6-iodo-1-hexylthio, 6,6,6- trichloro-1-hexylthio and dodecafluorohexylthio. Particularly preferred are chloromethyl- thio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, 2-fluoroethylthio, 2- chloroethylthio and 2,2,2-trifluoroethylthio.
The term "(Ci-C6-alkylthio)carbonyl" as used herein refers to a straight-chain or branched alkthio group (as mentioned above) having 1 to 6 carbon, preferably 1 to 4 carbon atoms (= Ci-C4-alkylthiocarbonyl) atoms attached via the carbon atom of the carbonyl group. Examples for Ci-C4-alkylthiocarbonyl include C(O)SCHs, C(OSC2H5, C(O)-SCH2-C2H5, C(O)SCH(CHs)2, n-butylthiocarbonyl, C(O)SCH(CHs)-C2H5, C(O)SCH2CH(CHs)2 and C(O)SC(CH3)s. Examples for d-Ce-alkylthiocarbonyl further encompass n-pentylthiocarbonyl, 1-methylbutylthiocarbonyl, 2-methylbutylthiocarbonyl, 3-methylbutylthiocarbonyl, 2,2-dimethylpropylthiocarbonyl, 1-ethylpropylthiocarbonyl, n- hexylthiocarbonyl, 1 ,1-dimethylpropylthiocarbonyl, 1 ,2-dimethylpropylthiocarbonyl, 1- methylpentylthiocarbonyl, 2-methylpentylthiocarbonyl, 3-methylpentylthiocarbonyl, 4- methylpentylthiocarbonyl, 1 ,1-dimethylbutylthiocarbonyl, 1 ,2-dimethylbutylthiocarbonyl, 1 ,3-dimethylbutythiocarbonyl, 2,2-dimethylbutylthiocarbonyl, 2,3-dimethylbutylthiocarbonyl, 3,3-dimethylbutylthiocarbonyl, 1-ethylbutlthioycarbonyl, 2-ethylbutylthiocarbonyl, 1 ,1 ,2-trimethylpropylthiocarbonyl, 1 ,2,2-trimethylpropylthio- carbonyl, 1-ethyl-1-methylpropylthiocarbonyl and 1-ethyl-2-methylpropylthiocarbonyl. The term "(Ci-C6-alkoxy)thiocarbonyl" as used herein refers to a straight-chain or branched alkoxy group (as mentioned above) having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkoxythiocarbonyl) attached via the carbon atom of the carbonyl group. Examples for Ci-C4-alkoxythiocarbonyl include C(S)OCHs, C(S)OC2H5, C(S)O-CH2-C2H5, C(S)OCH(CHs)2, n-butoxythiocarbonyl, C(S)OCH(CHs)-C2H5, C(S)OCH2CH(CHs)2 and C(S) OC(CH3)s. Examples for d-Ce-alkoxythiocarbonyl further encompass n-pentoxythiocarbonyl, 1-methylbutoxythiocarbonyl, 2- methylbutoxythiocarbonyl, 3-methylbutoxythiocarbonyl, 2,2- dimethylpropoxythiocarbonyl, 1-ethylpropoxythiocarbonyl, n-hexoxythiocarbonyl, 1 ,1- dimethylpropoxythiocarbonyl, 1 ,2-dimethylpropoxythiocarbonyl, 1-methylpentoxythiocarbonyl, 2-methylpentoxythiocarbonyl, 3- methylpentoxythiocarbonyl, 4-methylpentoxythiocarbonyl, 1 ,1- dimethylbutoxythiocarbonyl, 1 ,2-dimethylbutoxythiocarbonyl, 1 ,3-dimethylbutoxythiocarbonyl, 2,2-dimethylbutoxythiocarbonyl, 2,3- dimethylbutoxythiocarbonyl, 3,3-dimethylbutoxythiocarbonyl, 1 -ethylbutoxythiocarbonyl, 2-ethylbutoxythiocarbonyl, 1 ,1 ,2-trimethylpropoxythiocarbonyl, 1 ,2,2- trimethylpropoxythiocarbonyl, 1-ethyl-1-methylpropoxythiocarbonyl or 1 -ethyl-2- methylpropoxythiocarbonyl.
The term "Ci-C6-alkylsulfinyl" (Ci-C6-alkylsulfoxyl: Ci-C6-alkyl-S(=O)-), as used herein refers to a straight-chain or branched saturated alkyl group (as mentioned above) having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylsulfinyl) bonded through the sulfur atom of the sulfinyl group at any position in the alkyl group. Exam- pies for Ci-C4-alkylsulfinyl include S(O)CH3, S(O)C2H5, n-propylsulfinyl,
1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1 ,1-dimethylethylsulfinyl. Examples for Ci-Cβ-alkylsulfinyl further encompass n- pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 1 ,1- dimethylpropylsulfinyl, 1 ,2-dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl, 1- ethylpropylsulfinyl, n-hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3- methylpentylsulfinyl, 4-methylpentylsulfinyl, 1 ,1-dimethylbutylsulfinyl, 1 ,2- dimethylbutylsulfinyl, 1 ,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3- dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethy I buty I su If i ny I , 1 ,1 ,2-trimethylpropylsulfinyl, 1 ,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl and 1-ethyl-2-methylpropylsulfinyl.
The term "Ci-Cβ-alkylsulfonyl" (Ci-C6-alkyl-S(=O)2-) as used herein refers to a straight- chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylsulfonyl) (as mentioned above) which is bonded via the sulfur atom of the sulfonyl group at any position in the alkyl group. Examples for C1-C4- alkylsulfonyl include SO2-CH3, SO2-C2H5, n-propylsulfonyl, SO2--CH(CHs)2, n- butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and SO2-C(CHs)3. Exam- pies for Ci-Cβ-alkylsulfonyl further encompass n-pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1 ,1-dimethylpropylsulfonyl, 1 ,2- dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, n- hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4- methylpentylsulfonyl, 1 ,1-dimethylbutylsulfonyl, 1 ,2-dimethylbutylsulfonyl, 1 ,3- dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3- dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1 ,1 ,2- trimethylpropylsulfonyl, 1 ,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl and 1 -ethyl-2-methylpropylsulfonyl.
The term "Ci-Cβ-haloalkylsulfonyl" (Ci-C6-haloalkyl-S(=O)2-) as used herein refers to a straight-chain or branched saturated haloalkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-haloalkylsulfonyl) (as mentioned above) which is bonded via the sulfur atom of the sulfonyl group at any position in the alkyl group. Ex- amples for Ci-C4-haloalkylsulfonyl include chloromethylsulfonyl, dichloromethylsulfonyl, trichloromethylsulfonyl, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsul- fonyl, chlorofluoromethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsul- fonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2- iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2- fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3- fluoropropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2- chloropropylsulfonyl, 3-chloropropylsulfonyl, 2,3-dichloropropylsulfonyl, 2- bromopropylsulfonyl, 3-bromopropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3- trichloropropylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl, 1 -(fluoromethyl)-2 -fluoroethylsulfonyl, 1 -(chloromethyl)-2-chloroethylsulfonyl, 1 - (bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4- bromobutylsulfonyl, nonafluorobutylsulfonyl. Examples for Ci-Cβ-haloalkylsulfonyl further encompass 5-fluoro-1-pentylsulfonyl, 5-chloro-1-pentylsulfonyl, 5-bromo-1- pentylsulfonyl, 5-iodo-1-pentylsulfonyl, 5,5,5-trichloro-1-pentylsulfonyl, undecafluoro- pentylsulfonyl, 6-fluoro-1-hexylsulfonyl, 6-chloro-1-hexylsulfonyl, 6-bromo-1- hexylsulfonyl, 6-iodo-1-hexylsulfonyl, 6,6,6-trichloro-1-hexylsulfonyl and dodecafluoro- hexylsulfonyl. Particularly preferred are chloromethylsulfonyl, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl and 2,2,2-trifluoroethylsulfonyl.
The term "Ci-Cε-alkylamino" refers to a secondary amino group carrying one alkyl group as defined above, e.g. methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1 ,1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3-methylbutylamino, 2,2-dimethylpropylamino, 1-ethylpropylamino, hexylamino, 1 ,1-dimethylpropylamino, 1 ,2-dimethylpropylamino, 1-methylpentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1 ,1-dimethylbutylamino, 1 ,2-dimethylbutylamino, 1 ,3-dimethylbutylamino, 2,2-dimethylbutylamino, 2,3-dimethylbutylamino, 3,3-dimethylbutylamino, 1 -ethylbutylamino, 2-ethylbutylamino, 1 , 1 ,2-trimethylpropylamino, 1 ,2,2-trimethylpropylamino, 1 -ethyl-1 -methylpropylamino or 1 -ethyl- 2-methylpropylamino.
The term "di(Ci-C6-alkyl)amino)" refers to a tertiary amino group carrying two alkyl radicals as defined above, e.g. dimethylamino, diethylamino, di-n-propylamino, diiso- propylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-
N-methylamino, N-(n-butyl)-N-methylamino, N-(n-pentyl)-N-methylamino, N-(2-butyl)- N-methylamino, N-(isobutyl)-N-methylamino, N-(n-pentyl)-N-methylamino, N-(n-propyl)- N-ethylamino, N-(isopropyl)-N-ethylamino, N-(n-butyl)-N-ethylamino, N-(n-pentyl)- N-ethylamino, N-(2-butyl)-N-ethylamino, N-(isobutyl)-N-ethylamino or N-(n-pentyl)- N-ethylamino.
The term "C2-C6-alkenyl" as used herein and in the alkenyl moieties of C2-C6-alkenyloxy, C2-C6-alkenylamino, C2-C6-alkenylthio, C2-C6-alkenylsulfonyl, (C2-C6-alkenyl)carbonyl, (C2-C6-alkenyloxy)carbonyl and (C2-C6-alkenyl)carbonyloxy refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl; 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1-dimethyl-2-propenyl, 1 ,2-dimethyl- 1-propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl-1 -propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1-dimethyl-2-butenyl, 1 ,1-dimethyl- 3-butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1-butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl- 3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl-1 -butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1-ethyl-2-methyl-1 -propenyl and 1-ethyl-2-methyl-2-propenyl.
The term, "C2-C6-alkenyloxy" as used herein refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as vinyloxy, allyloxy (propen-3-yloxy), methallyloxy, buten-4-yloxy, etc.
The term "C2-C6-alkenylthio" as used herein refers to a straight-chain or branched al- kenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example vinylsulfanyl, allylsulfanyl (propen-3-ylthio), methallylsufanyl, buten-4-ylsulfanyl, etc..
The term "C2-C6-alkenylcarbonyl" as used herein refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is bonded via the carbon atom of the carbonyl group at any bond in the alkenyl group, for example vinylcarbonyl, allylcarbonyl (propen-3-ylcarbonyl), methallylcarbonyl, buten-4- ylcarbonyl, etc..
The term "C2-C6-alkenyloxycarbonyl" as used herein refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is bonded via the carbon atom of the oxycarbonyl group (RO-C(O)-; R = C2-C6-alkenyl), for example vinyloxycarbonyl, allyloxycarbonyl (propen-3-yloxycarbonyl), methallyloxy- carbonyl, buten-4-yloxycarbonyl, etc..
The term "C2-C6-alkenylcarbonyloxy" as used herein refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is bonded via the oxygen atom of the carbonyloxy group (R-C(O)-O-; R = C2-C6-alkenyl), for example vinylcarbonyloxy, allylcarbonyloxy (propen-3-ylcarbonyloxy), methallylcar- bonyloxy, buten-4-ylcarbonyloxy, etc..
The term "C2-C6-alkenylamino" as used herein refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example vinylamino, allylamino (propen-3-ylamino), methallylamino, buten-4-ylamino, etc.
The term "C2-C6-alkenylsulfonyl" as used herein refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfonyl (SO2) group, for example vinylsulfonyl, allylsulfonyl (propen-3-ylsulfonyl), methallylsufonyl, buten-4-ylsulfonyl, etc.
The term "C2-C6-alkynyl" as used herein and in the alkynyl moieties of C2-C6-alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio, C2-C6-alkynylsulfonyl, C2-C6-alkynylcarbonyl, C2-C6-alkynyloxycarbonyl and Ci-Cβ-alkynylcarbonyloxy refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1-yn-1-yl, prop-2- yn-1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent-1-yn-1- yl, n-pent-1-yn-3-yl, n-pent-1-yn-4-yl, n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4- yl, n-pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-1-yl, n- hex-1-yn-3-yl, n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex- 2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3- methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1- yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl or 4-methylpent-2-yn-5-yl and the like.
The term, "C2-C6-alkynyloxy" as used herein refers to a straight-chain or branched al- kynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as propargyloxy (propyn-3-yloxy), butyn-3-yloxy, and butyn-4-yloxy.
The term "C2-C6-alkynylthio" as used herein refers to a straight-chain or branched al- kynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, such as propargylsulfanyl (propyn-3-ylthio), butyn-3-ylsufanyl and butyn- 4-ylsulfanyl.
The term "C2-C6-alkynylcarbonyl" as used herein refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is bonded via the carbon atom of the carbonyl group at any bond in the alkynyl group, for example propargylcarbonyl (propyn-3-ylcarbonyl), butyn-3-ylcarbonyl, and butyn-4-ylcarbonyl.
The term "C2-C6-alkynyloxycarbonyl" as used herein refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is bonded via the carbon atom of the oxycarbonyl group (RO-C(O)-; R = C2-C6-alkynyl), for example propargyloxycarbonyl (propyn-3-yloxycarbonyl), butyn-3-yloxycarbonyl, and butyn-4-yloxycarbonyl.
The term "C2-C6-alkynylcarbonyloxy" as used herein refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is bonded via the oxygen atom of the carbonyloxy group (R-C(O)-O-; R = C2-C6-alkynyl), for example propargylcarbonyloxy (propyn-3-ylcarbonyloxy), butyn-3-ylcarbonyloxy, and butyn-4-ylcarbonyloxy.
The term "C2-C6-alkynylamino" as used herein refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, such as propargylamino (propyn-3-ylamino), butyn-3-amino, and butyn- 4-ylamino.
The term "C2-C6-alkynylsulfonyl" as used herein refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfonyl (SO2) group, such as propargylsulfonyl (propin-3-yltsulfonyl), butin-3-ylsufonyl and butin-4-ylsulfonyl.
The term "C3-Ci2-cycloalkyl" as used herein refers to a mono- or bi- or polycyclic hy- drocarbon radical having 3 to 8 carbon atoms (= Cs-Cs-cycloalkyl), in particular 3 to 6 carbon atoms (= Cs-Cβ-cycloalkyl). Examples of monocyclic radicals comprise cyclo- propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicy- clo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
The term "Cs-Cβ-halocycloalkyl" as used herein refers to a monocyclic hydrocarbon radical having 3 to 6 carbon atoms, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Examples are 1- and 2- fluoro- cyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3- tetrafluorocyclpropyl, 1- and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1-,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1-,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-dichlorocyclopentyl and the like.
The term "Cs-Cβ-cycloalkoxy" as used herein refers to a monocyclic hydrocarbon radical having 3 to 6 carbon atoms which is bound via an oxygen atom. Examples include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy and cyclohexyloxy.
The term "aryl" as used herein refers to a Cβ-C-u carboaromatic group, such as phenyl, Naphthyl, anthracenyl and phenanthrenyl. Preferably, aryl is phenyl.
The term "aryl-Ci-C4-alkyl" as used herein refers to aryl as defined above which is bound via a Ci-C4-alkyl group, in particular a methyl or an ethyl group, to the remainder of the molecule. Examples are benzyl, 2-phenylethyl, naphthylmethyl and the like.
The term "aryl-Ci-C4-alkoxy" as used herein refers to aryl-Ci-C4-alkyl as defined above which is bound via an oxygen atom to the remainder of the molecule (aryl-Ci-C4-alkyl- O-). One example is benzoxy.
The term "aryloxy" refers to aryl as defined above which is bound via an oxygen atom to the remainder of the molecule. Examples are phenoxy and naphthoxy.
The term "arylcarbonyl" refers to aryl as defined above which is bound via the C atom of a carbonyl group to the remainder of the molecule. Examples are benzoyl and naphthylcarbonyl. The term "aryloxycarbonyl" refers to aryl as defined above which is bound via the C atom of an oxycarbonyl group to the remainder of the molecule (Ar-O-C(O)-; Ar = hetaryl).
Phenyl fused to phenyl is naphthyl.
Phenyl fused to a 5- or 6-membered non-aromatic (i.e. saturated or partially unsaturated) heterocyclic ring is for example 2,3-dihydrobenzofuranyl, benzoxolanyl, 2,3- dihydrobenzothienyl, indolinyl, chromanyl, chromenyl, benzodioxanyl and the like. Ex- amples for phenyl fused to a 5- or 6-membered aromatic heterocyclic ring (= fused to a 5- or 6-membered heteroaromatic ring) are given below.
The term "hetaryl/heteroaromatic ring" as used herein refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, which may be fused to a carbocyc- lie or heterocyclic 5, 6 or 7 membered ring thus having a total number of ring members from 8 to 10, wherein in each case 1 , 2, 3 or 4, preferably 1 , 2 or 3, of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. The carbocyclic or heterocyclic fused ring is selected from C5-C7-cycloalkyl, C5-C7- cycloalkenyl, 5 to 7 membered heterocyclyl and phenyl.
Examples for monocyclic 5- to 6-membered heteroaromatic rings include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl and isoxa- zolyl.
Examples for 5- to 6-membered heteroaromatic rings being fused to a phenyl ring (or for a phenyl ring fused to a 5- to 6-membered heteroaromatic ring) are quinolinyl, iso- quinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl, and benzimidazolyl. Examples for 5- to 6-membered heteroaromatic rings being fused to a cycloalkenyl ring are dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydrochinolinyl, dihydroiso- chinolinyl, chromenyl, chromanyl and the like.
The term "hetaryl-Ci-C4-alkyl" refers to hetaryl as defined above which is bound via a Ci-C4-alkyl group, in particular a methyl group (= hetaryl methyl), to the remainder of the molecule.
The term "hetaryloxy" refers to hetaryl as defined above which is bound via an oxygen atom to the remainder of the molecule. The term "hetarylcarbonyl" refers to hetaryl as defined above which is bound via the C atom of a carbonyl group to the remainder of the molecule.
The term "hetaryloxycarbonyl" refers to hetaryl as defined above which is bound via the C atom of an oxycarbonyl group to the remainder of the molecule (Het-O-C(O)-; Het = hetaryl).
The term "hetarylmethylcarbonyl" refers to hetarylmethyl as defined above which is bound via the C atom of a carbonyl group to the remainder of the molecule (Het-CH2-C(O)-; Het = hetaryl).
The term "(saturated, partially unsaturated or aromatic) 5 or 6-membered heterocyclic ring/ heterocyclyl" comprises heteroaromatic rings as defined above and nonaromatic saturated or partially unsaturated heterocyclic rings having 5 or 6 ring members and 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms as ring members. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. Examples for non-aromatic rings include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3- dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1 ,3- and 1 ,4- dioxanyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothiopyranyl, morpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-only, pyrrolidin-2,5-dionyl, imidazolidin-2-only, oxa- zolidin-2-only, thiazolidin-2-only and the like.
The term "5-, 6- or 7-membered carbocycle" comprises monocyclic aromatic rings and nonaromatic saturated or partially unsaturated carbocyclic rings having 5, 6 or 7 ring members. Examples for non-aromatic rings include cyclopentyl, cyclopentenyl, cyclopentadienyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cyclohep- tenyl, cycloheptadienyl and the like.
The term "linear (Ci-C6)-alkandiyl" as used herein refers to methylendiyl, ethane- 1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl, hexane-1 ,6-diyl.
The term " (C2-C5)-alkandiyl" as used herein refers to alkylene groups such as ethane- 1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl or pentane-1 ,5-diyl, where a part or all hydrogen atoms of the alkylene groups may be substituted as defined above. If one or two of the methylene groups are replaced by O, S or NR, the term also encompasses for example -0-CH2-, -S-CH2-, -NR-CH2-, -0-CH2-CH2-, -S-CH2-CH2-, -NR-CH2-CH2-, -CH2-O-CH2-, -CH2-S-CH2TCH2-NR-CH2-, -0-CH2-O-, -S-CH2-S-, -NR-CH2-NR-, -0-CH2-CH2-CH2-, -S-CH2-CH2-CH2-, -NR-CH2-CH2-CH2-, -CH2-O-CH2-CH2-, -CH2-S-CH2-CH2-, -CH2-NR-CH2-CH2-, -0-CH2-CH2-O-, -S-CH2-CH2-S-, -NR-CH2-CH2-NR-, -0-CH2-CH2-CH2-CH2-, -S-CH2-CH2-CH2-CH2-, -NR-CH2-CH2-CH2-CH2-, -CH2-O-CH2-CH2-CH2-, -CH2-S-CH2-CH2-CH2-, -CH2-NR-CH2-CH2-CH2-, -CH2-CH2-O-CH2-CH2-, -CH2-CH2-S-CH2-CH2-, -CH2-CH2-NR-CH2-CH2-, -0-CH2-CH2-CH2-O-, -S-CH2-CH2-CH2-S-, -NR-CH2-CH2-CH2-NR- and the like. Here, too, a part or all hydrogen atoms of the methylene groups may be substituted as defined above.
The remarks made below as to preferred embodiments of the variables of the compounds (I), of the features of the use and method according to the invention and of the composition of the invention are valid on their own as well as - preferably - in combination with each other.
R1 is preferably selected from the group consisting of hydrogen, cyano, Ci-Cβ-alkyl, Ci- Cβ-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Cβ-alkoxycarbonyl, Cs-Cβ-cycloalkyl, phenyl, benzyl, phenoxycarbonyl, 5- or 6-membered hetaryl and 5- or 6-membered hetarylmethyl each of the six last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb1.
More preferably, R1 is selected from the group consisting of hydrogen, Ci-Cβ-alkyl, Ci- Cβ-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, benzyl, 5- or 6-membered hetaryl and 5- or 6-membered hetarylmethyl, where each of the last four mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2 radicals Rb1.
Even more preferably, R1 is selected from the group consisting of hydrogen, C-i-Cβ- alkyl, phenyl and benzyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2 radicals Rb1.
In a particularly preferred embodiment, R1 is hydrogen.
In an alternatively preferred embodiment, R1 is different from hydrogen. Particularly, R1 is in this case selected from Ci-Cβ-alkyl, d-Cβ-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, benzyl, 5- or 6-membered hetaryl and 5- or 6-membered hetarylmethyl, where each of the last four mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2 radicals Rb1. More particularly, R1 is in this case selected from Ci-Cβ-alkyl, phenyl and benzyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2 radicals Rb1. Rb1 is preferably selected from halogen, hydroxy, amino, d-Cε-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy, d-Cβ-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylamino, di(Ci-C6-alkyl)amino, Ci-Cβ-alkylsulfonyl, CrCβ-alkylcarbonyl, CrCβ-alkoxycarbonyl and CrCβ- alkylcarbonyloxy and more preferably from halogen, CrCβ-alkyl, Ci-C6-haloalkyl, Cr Cβ-alkoxy and Ci-C6-haloalkoxy.
The variables R2a or R2b are preferably selected from the group consisting of hydrogen, d-d-alkyl, formyl, CN, C(S)NRaRb, d-Ce-alkylcarbonyl, Ci-d-haloalkylcarbonyl, d- Cβ-alkoxycarbonyl, Ci-d-alkoxy-Ci-d-alkoxycarbonyl, d-Cβ-alkylthiocarbonyl, ben- zoyl, 5 or 6 membered hetarylcarbonyl, each of the last two mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 Rb2. More preferably R2a or R2b is hydrogen. In another preferred embodiement R2a and R2b are selected from the group consisting of oxazolyl, thiazolyl and imidazolyl.
Independently of each other, the variables R2a and R2b are preferably selected from hydrogen, d-C6-alkyl, formyl, CN, C(S)NRaRb, d-Ce-alkylcarbonyl, CrC6- haloalkylcarbonyl, d-Cβ-alkoxycarbonyl, Crd-alkoxy-d-d-alkoxycarbonyl, CrCβ- alkylthiocarbonyl, phenyl, benzoyl, benzyl, benzylcarbonyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroa- toms selected from O, S and N as ring members, hetarylmethyl, hetarylcarbonyl and hetarylmethylcarbonyl, wherein each of the 8 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals Rb2, and wherein the het- eroaromatic ring in hetarylmethyl, hetarylcarbonyl and hetarylmethylcarbonyl is 5- or 6- membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring members.
More preferably, R2a and R2b are selected from hydrogen, CrCβ-alkyl, formyl, CN, C(S)NRaRb, d-Ce-alkylcarbonyl, Ci-Ce-haloalkylcarbonyl, d-Ce-alkoxycarbonyl, CrC4- alkoxy-Ci-d-alkoxycarbonyl, d-Cβ-alkylthiocarbonyl, benzoyl, benzylcarbonyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, hetarylcarbonyl and hetarylmethylcarbonyl, wherein each of the 5 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals Rb2, and wherein the het- eroaromatic ring in hetarylcarbonyl and hetarylmethylcarbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring members.
In an even more preferred embodiment, R2a is selected from hydrogen, Ci-C6-alkyl, formyl, CN, C(S)NRaRb, d-Ce-alkylcarbonyl, Ci-Ce-haloalkylcarbonyl, CrC6- alkoxycarbonyl, Crd-alkoxy-d-d-alkoxycarbonyl, d-Cβ-alkylthiocarbonyl, benzoyl, benzylcarbonyl, hetarylcarbonyl and hetarylmethylcarbonyl, wherein each of the 4 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals Rb2, and wherein the heteroaromatic ring in hetarylcarbonyl and hetarylmethyl- carbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroa- toms selected from oxygen, sulfur and nitrogen as ring members.
Particularly, R2a is selected from hydrogen, Ci-Cβ-alkyl, CN, d-Cβ-alkylcarbonyl, Ci-Cβ- haloalkylcarbonyl, benzoyl and hetarylcarbonyl, wherein the 2 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals Rb2, and wherein the heteroaromatic ring in hetarylcarbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring members. Specifically, R2a is hydrogen or Ci-Cβ-alkyl, and more specifically hydrogen.
In an even more preferred embodiment, R2b is selected from hydrogen, Ci-Cβ-alkyl, formyl, CN, C(S)NRaRb, d-Ce-alkylcarbonyl, d-Ce-haloalkylcarbonyl, CrC6- alkoxycarbonyl,
Figure imgf000027_0001
Ci-Cβ-alkylthiocarbonyl, benzoyl, benzylcarbonyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, hetarylcarbonyl and hetarylmethylcarbonyl, wherein each of the 5 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals Rb2, and wherein the heteroaromatic ring in hetarylcarbonyl and hetarylmethylcarbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring members.
Particularly, R2b is selected from hydrogen, Ci-Cβ-alkyl, CN, Ci-Cβ-alkylcarbonyl, C-i-Cβ- haloalkylcarbonyl, benzoyl, hetarylcarbonyl, wherein the 2 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals Rb2, and wherein the heteroaromatic ring in hetarylcarbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring members; and a 5- or 6-membered saturated, partially unsaturated or aromatic hetero- cyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members which may carry any combination of 1 , 2 or 3 radicals Rb2. More particularly, R2b is selected from hydrogen, Ci-Cβ-alkyl and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members which may carry any combination of 1 , 2 or 3 radicals Rb2. Even more particularly, R2b is H or a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members which may carry any combination of 1 , 2 or 3 radicals Rb2. Specifically, R2b is a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members which may carry any combination of 1 , 2 or 3 radicals Rb2. The 5- or 6-membered heterocyclic ring R2b is preferably non-aromatic, i.e. saturated or partially unsaturated, and more preferably partially unsaturated. Preferably, the 5- or 6- membered heterocyclic ring R2b is unsubstituted. Preferably, the 5- or 6-membered heterocyclic ring R2b is 5-membered and contains two heteroatoms. More preferably, the 5- or 6-membered heterocyclic ring R2b is selected from oxazolinyl and thiazolinyl, more preferably oxazolinyl and thiazolinyl which are bound in the 2-position (with respect to the 1 -position of O and S, respectively, and to the 3-position of N), and specifically R2b is thiazolinyl which is preferably bound in the 2-position.
Rb2 is preferably selected from halogen, hydroxy, amino, d-Cε-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy, d-Cβ-haloalkoxy, d-Cβ-alkylthio, d-Cβ-alkylamino, di(Ci-C6-alkyl)amino, Ci-Cβ-alkylsulfonyl, d-Cβ-alkylcarbonyl, d-Cβ-alkoxycarbonyl and d-Cβ- alkylcarbonyloxy and more preferably from halogen, d-Cβ-alkyl, d-Cβ-haloalkyl, Ci- Cβ-alkoxy and Ci-C6-haloalkoxy.
In another preferred embodiment of the invention the radicals R1 and R2b together form a bridging bivalent carbonyl group C(O).
R2c and R2d, independently of each other, are preferably selected from hydrogen, for- myl, d-Cβ-alkyl, d-Cβ-alkylcarbonyl, d-Cβ-alkylthiocarbonyl, d-Cβ-alkoxycarbonyl, Ci-Cβ-alkoxythiocarbonyl, arylcarbonyl, hetarylcarbonyl, aryloxycarbonyl and hetary- loxycarbonyl, where the aliphatic, aromatic or heteroaromatic moieties in the 9 last- mentioned radicals may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 radicals Rc2, and where hetaryl is a 5- or 6-membered heteroaromatic ring containing 1 , 2, 3 or 4 het- eroatoms selected from O, S and N as ring members. More preferably, R2c and R2d are hydrogen.
Among compounds of general formula (I) preference is given to compounds wherein each of the radicals R3a, R3b, R3c and R3d is hydrogen.
Preference is given to compounds of general formula (I) wherein the radicals R4a, R4b, R4c and R4d are independently selected from the group consisting of hydrogen, halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, 5- or 6- membered hetaryl, 5- or 6-membered hetarylmethyl and benzyl wherein the four last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb4.
More preferably, R4a, R4b, R4c and R4d are independently selected from the group consisting of hydrogen, halogen, d-Cβ-alkyl, d-Cβ-haloalkyl, phenyl and benzyl wherein the phenyl moiety in the 2 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 radicals Rb4. In a particular embodiment of the invention, all radicals R4a, R4b, R4c and R4d are hydrogen.
In an alternative particular embodiment, at least one of the radicals R4a, R4b, R4c and R4d is different from hydrogen.
In this particular embodiment, R4a and/or R4c is/are preferably different from hydrogen. Particular preference is given to compounds (I) wherein R4a and/or R4c is/are selected from the group consisting of halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, phenyl and benzyl which may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 radicals Rb4. In this particular embodiment, R4b and R4d and optionally one of R4a and R4c are preferably hydrogen or Ci-Cβ-alkyl and more preferably hydrogen.
In another preferred embodiment of the invention, the radicals R2a and R4a together form a bridging bivalent radical. Preferred examples of such bridging radicals are
C(O)-CH2, C(S)-CH2, CH2-CH2, S(O)2-CH2, S(O)-CH2, C(O)-O, C(S)-O, S(O)2-O, S(O)- O, C(O)-NH, C(S)-NH, S(O)2-NH, S(O)-NH, wherein the last eight mentioned radicals are attached to the nitrogen atom via the carbonyl group, the thiocarbonyl group or the sulphur atom respectively. More preferred examples of such radicals are C(O)-CH2, C(S)-CH2, CH2-CH2, S(O)2-CH2, S(O)-CH2.
Likewise preferred are compounds of general formula (I), wherein R4a together with R4b and/or R4c together with R4d form a radical =0, =NRC or =CRdRe. Preferably, the radicals Rc, Rd and Re are selected from the group consisting of hydrogen, Ci-Cβ-alkyl, phenyl, hydroxy, Ci-Cβ-alkoxy, Ci-Cβ-alkylamino and di-(Ci-C6-alkyl)amino.
Rb4 is preferably selected from halogen, hydroxy, amino, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy, d-Cβ-haloalkoxy, d-Cβ-alkylthio, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, Ci-Cβ-alkylsulfonyl, Ci-Cβ-alkylcarbonyl, Ci-Cβ-alkoxycarbonyl and C-i-Cβ- alkylcarbonyloxy and more preferably from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, Ci- Cβ-alkoxy and d-Cβ-haloalkoxy.
Specifically, all radicals R4a, R4b, R4c and R4d are hydrogen.
Preferably, each RZ1 is independently selected from the group consisting of halogen, OH, SH, d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkoxy, Ci-Ce-haloalkoxy, d-Ce-alkylthio and Ci-Cβ-haloalkylthio, more preferably from halogen, Ci-Cβ-alkyl, Ci-C6-haloalkyl, Ci- Cβ-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio and d-Cβ-haloalkylthio and specifically from halogen Ci-C6-alkoxy and Ci-C6-haloalkoxy.
In one preferred embodiment, n is O or 1. In an alternatively preferred embodiment, n is 2.
In one preferred embodiment of the present invention the variable X in compounds of the general formula (I) is sulfur. In another preferred embodiment X is O. In yet another preferred embodiment X is NR5. Particularly preferably, X is S.
In one preferred embodiment of the present invention the variable Y in compounds of the general formula (I) is sulfur. In another preferred embodiment Y is O. In yet another preferred embodiment Y is NR5a. Particularly preferably, Y is S.
R5 and R5a are preferably selected from hydrogen, Ci-Cβ-alkyl, formyl, CN, C(O)NRaRb, C(S)NRaRb, C-i-Ce-alkylcarbonyl, d-Ce-haloalkylcarbonyl, d-Ce-alkoxycarbonyl, Ci-C4- alkoxy-Ci-d-alkoxycarbonyl, Ci-Cβ-alkylthiocarbonyl, benzoyl, and hetarylcarbonyl, wherein each of the 2 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals Rb5, and wherein the heteroaromatic ring in hetarylcarbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroa- toms selected from oxygen, sulfur and nitrogen as ring members. More preferably, R5 and R5a are hydrogen or Ci-Cβ-alkyl.
Rb5 is preferably selected from halogen, hydroxy, amino, Ci-Cβ-alkyl, d-Cβ-haloalkyl, Ci-Cβ-alkoxy, Ci-Cβ-haloalkoxy, d-Cβ-alkylthio, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, Ci-Cβ-alkylsulfonyl, Ci-Cβ-alkylcarbonyl, Ci-Cβ-alkoxycarbonyl and C-i-Cβ- alkylcarbonyloxy and more preferably from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, Ci- Cβ-alkoxy and d-Cβ-haloalkoxy.
T is preferably selected from -ORT1 and -0-C(O)-R1"3.
RT1 is preferably selected from hydrogen and Ci-C6-alkyl. More preferably, RT1 is hydrogen.
RT3 is preferably selected from Ci-Cβ-alkyl which may carry 1 , 2 or 3 substituents RTa; C3-C6-cycloalkyl which may carry 1 , 2 or 3 substituents RTb; phenyl which may carry 1 , 2 or 3 substituents RTc; naphthyl which may carry 1 , 2 or 3 substituents RTc; benzo-1 ,3- dioxolanyl which may carry 1 , 2 or 3 substituents RTc; and 5- or 6-membered hetaryl containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, which may carry 1 , 2 or 3 substituents RTd.
Preferably, each RTa is independently selected from the group consisting of halogen, d-d-alkoxy, d-d-haloalkoxy, d-d-alkylthio, d-d-haloalkylthio, Ci-C4- alkylcarbonyl, Ci-d-haloalkylcarbonyl, Ci-d-alkoxycarbonyl, C1-C4- haloalkoxycarbonyl, Ci-d-alkylcarbonyloxy, Ci-d-haloalkylcarbonyloxy, phenyl, phenyloxy, and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the 3 last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyloxy and CrC4- haloalkylcarbonyloxy. More preferably, each RTa is independently selected from the group consisting of Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-alkylcarbonyl, CrC4- alkoxycarbonyl, phenyl, phenyloxy, and 5- or 6-membered hetaryl.
Preferably, each RTb is independently selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, CrC4- haloalkylthio, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, Cr C4-haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, Ci-C4-haloalkylcarbonyloxy, phenyl, phenyloxy, and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the 3 last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyloxy and CrC4- haloalkylcarbonyloxy.
Preferably, each RTc is independently selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, CrC4- haloalkylthio, CrC^alkylcarbonyl, CrC^haloalkylcarbonyl, CrC^alkoxycarbonyl, Cr C4-haloalkoxycarbonyl, CrC^alkylcarbonyloxy, and CrC^haloalkylcarbonyloxy and 5- or 6-membered hetaryl, where the hetaryl ring may carry 1 , 2 or 3 substituents selected from halogen, CrC4-alkyl, CrC4-haloalkyl, CrC^alkylcarbonyloxy and CrC4- haloalkylcarbonyloxy.
Preferably, each RTd is independently selected from the group consisting of halogen, CrC4-alkyl, CrC4-haloalkyl, d-C4-alkoxy, CrC4-haloalkoxy, CrC4-alkylthio, CrC4- haloalkylthio, CrC^alkylcarbonyl, CrC^haloalkylcarbonyl, CrC^alkoxycarbonyl, Cr C4-haloalkoxycarbonyl, d-C^alkylcarbonyloxy, CrC^haloalkylcarbonyloxy, phenyl, phenyloxy, and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the 3 last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, CrC4-alkyl, CrC4-haloalkyl, CrC^alkylcarbonyloxy and CrC4- haloalkylcarbonyloxy. More preferably, each RTd is independently selected from the group consisting of halogen, CrC4-alkyl, CrC4-haloalkyl, CrC4-alkoxy, CrC4- haloalkoxy, Ci-C4-alkylthio, CrC4-haloalkylthio, CrC^alkylcarbonyl, CrC4- haloalkylcarbonyl, CrC^alkoxycarbonyl, CrC^haloalkoxycarbonyl, CrC4- alkylcarbonyloxy, CrC^haloalkylcarbonyloxy and phenyl, where the phenyl moiety may carry 1 , 2 or 3 substituents selected from halogen, CrC4-alkyl, CrC4-haloalkyl, CrC^alkylcarbonyloxy and CrC^haloalkylcarbonyloxy.
In one preferred embodiment, Z is a group of formula (I I. A) or (II. B). Preferred mean- ings of the variables in theses groups are listed above. Compounds (I) wherein Z is a group of formula (I I. A) or (II. B) represent tautomers in case R2a and R2b are hydrogen.
In an alternatively preferred embodiment, Z is a group of formula (II. C). Preferred meanings of the variables in theses groups are listed above.
Compounds (I) wherein Z is a group of formula (II. C) can serve as intermediates in the preparation of compounds (I) wherein Z is a group of formula (I I. A) or (II. B). For example, in compounds (I) wherein T is a group -O-RT1, the group T can be converted into a leaving group, especially if RT1 is H, e.g. by converting it into the corresponding tosylate or halogenide. Compounds (I) wherein T is a group -O-C(O)-RT3 can be reacted directly to the corresponding compound (I) wherein Z is a group (I I. A) or (II. B). However, compounds (I) wherein Z is a group of formula (II. C) have themselves a good activity profile against harmful animal pests and can thus be used without further conversion.
Particularly preferred compounds (I) are those of the formulae (I.A.1), (I.A.2), (I.B.1), (I.B.2), (I.C.1 ), (I.C.2), (I.C.3) and (I.C.4) below:
Figure imgf000032_0001
(I.A.1 ) (I.B.1 )
Figure imgf000032_0002
(I.A.2) (I.B.2)
Figure imgf000032_0003
(I.C.1 ) (I.C.2)
Figure imgf000033_0001
(I.C.3) (I.C.4)
in which the variables R1, R2a, R2b, R4a, R4b, RZ1, RT3, X, Y and n have the general or preferred meanings given above.
Examples of particularly preferred compounds of the general formula I are the compounds I compiled in Tables 1 to 176 below. Moreover, the meanings mentioned for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table 1
Compounds of the formulae (I.A.1 ) or (I.B.1 ) and their mixtures, wherein X is O, R1 is hydrogen, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 2
Compounds of the formulae (I.A.1) or (I.B.1) and their mixtures, wherein X is S, R1 is hydrogen, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 3
Compounds of the formulae (I.A.1) or (I.B.1) and their mixtures, wherein X is NH, R1 is hydrogen, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 4
Compounds of the formulae (I.A.1) or (I.B.1) and their mixtures, wherein X is NCH3, R1 is hydrogen, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 5
Compounds of the formulae (I.A.1 ) or (I.B.1 ) and their mixtures, wherein X is O, R1 is CH3, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A. Table 6
Compounds of the formulae (LA.1 ) or (I.B.1) and their mixtures, wherein X is S, R1 is CH3, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 7
Compounds of the formulae (LA.1 ) or (I.B.1) and their mixtures, wherein X is NH, R1 is CH3, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 8
Compounds of the formulae (LA.1 ) or (I.B.1 ) and their mixtures, wherein X is NCH3, R1 is CH3, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 9
Compounds of the formulae (I.A.1 ) or (I.B.1 ) and their mixtures, wherein X is O, R1 is phenyl, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 10
Compounds of the formulae (I.A.1 ) or (I.B.1 ) and their mixtures, wherein X is S, R1 is phenyl, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 11
Compounds of the formulae (I.A.1) or (I.B.1) and their mixtures, wherein X is NH, R1 is phenyl, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 12
Compounds of the formulae (I.A.1) or (I.B.1) and their mixtures, wherein X is NCH3, R1 is phenyl, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 13
Compounds of the formulae (I.A.1 ) or (I.B.1 ) and their mixtures, wherein X is O, R1 is benzyl, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a com- pound corresponds in each case to one row of table A.
Table 14
Compounds of the formulae (LA.1 ) or (I.B.1) and their mixtures, wherein X is S, R1 is benzyl, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 15
Compounds of the formulae (LA.1) or (I.B.1) and their mixtures, wherein X is NH, R1 is benzyl, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 16
Compounds of the formulae (LA.1) or (I.B.1) and their mixtures, wherein X is NCH3, R1 is benzyl, R2a or R2b is hydrogen, and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Tables 17 to 32
Compounds of the formulae (LA.1 ) or (I.B.1 ) and their mixtures, wherein the combina- tion of X and R1 is as defined in any of Tables 1 to 16, the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of Table A and R2a or R2b is CH3 instead of hydrogen.
Tables 33 to 48 Compounds of the formulae (LA.1 ) or (I.B.1 ) and their mixtures, wherein the combination of X and R1 is as defined in any of Tables 1 to 16, the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of Table A and R2a or R2b is -C(O)CH3 instead of hydrogen.
Tables 49 to 64
Compounds of the formulae (LA.1 ) or (I.B.1 ) and their mixtures, wherein the combination of X and R1 is as defined in any of Tables 1 to 16, the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of Table A and R2a or R2b is benzoyl instead of hydrogen.
Tables 65 to 80
Compounds of the formulae (LA.1 ) or (I.B.1 ) and their mixtures, wherein the combination of X and R1 is as defined in any of Tables 1 to 16, the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of Table A and R2a or R2b is thiazolin-2-yl instead of hydrogen. Tables 81 to 96
Compounds of the formulae (I.A.1 ) or (I.B.1 ) and their mixtures, wherein the combination of X and R1 is as defined in any of Tables 1 to 16, the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of Table A and R2a or R2b is oxazolin-2-yl instead of hydrogen.
Tables 97 to 1 12
Compounds of the formulae (I.A.1 ) or (I.B.1 ) and their mixtures, wherein the combination of X and R1 is as defined in any of Tables 1 to 16, the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of Table A and R2a or R2b is imidazolin-2-yl instead of hydrogen.
Table 113
Compounds of the formula (I.C.1), wherein Y is O, R1 is hydrogen and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 114
Compounds of the formula (I.C.1), wherein Y is S, R1 is hydrogen and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 115
Compounds of the formula (I.C.1), wherein Y is NH, R1 is hydrogen and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 116
Compounds of the formula (I.C.1), wherein Y is NCH3, R1 is hydrogen and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 117
Compounds of the formula (I.C.1), wherein Y is O, R1 is CH3 and the combination of
(Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 118
Compounds of the formula (I.C.1), wherein Y is S, R1 is CH3 and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 119 Compounds of the formula (I.C.1), wherein Y is NH, R1 is CH3 and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 120
Compounds of the formula (I.C.1), wherein Y is NCH3, R1 is CH3 and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 121
Compounds of the formula (I.C.1), wherein Y is O, R1 is phenyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 122
Compounds of the formula (I.C.1), wherein Y is S, R1 is phenyl and the combination of
(Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 123
Compounds of the formula (I.C.1), wherein Y is NH, R1 is phenyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 124 Compounds of the formula (I.C.1), wherein Y is NCH3, R1 is phenyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 125 Compounds of the formula (I.C.1), wherein Y is O, R1 is benzyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 126
Compounds of the formula (I.C.1), wherein Y is S, R1 is benzyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 127
Compounds of the formula (I.C.1), wherein Y is NH, R1 is benzyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 128
Compounds of the formula (I.C.1), wherein Y is NCH3, R1 is benzyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 129
Compounds of the formula (I. C.2), wherein Y is O, R1 is hydrogen and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 130
Compounds of the formula (I. C.2), wherein Y is S, R1 is hydrogen and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 131
Compounds of the formula (I. C.2), wherein Y is NH, R1 is hydrogen and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 132
Compounds of the formula (I. C.2), wherein Y is NCH3, R1 is hydrogen and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 133
Compounds of the formula (I. C.2), wherein Y is O, R1 is CH3 and the combination of
(Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 134
Compounds of the formula (I. C.2), wherein Y is S, R1 is CH3 and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 135 Compounds of the formula (I. C.2), wherein Y is NH, R1 is CH3 and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 136
Compounds of the formula (I. C.2), wherein Y is NCH3, R1 is CH3 and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 137
Compounds of the formula (I. C.2), wherein Y is O, R1 is phenyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 138
Compounds of the formula (I. C.2), wherein Y is S, R1 is phenyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 139
Compounds of the formula (I. C.2), wherein Y is NH, R1 is phenyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 140
Compounds of the formula (I. C.2), wherein Y is NCH3, R1 is phenyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 141
Compounds of the formula (I. C.2), wherein Y is O, R1 is benzyl and the combination of
(Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 142
Compounds of the formula (I. C.2), wherein Y is S, R1 is benzyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 143 Compounds of the formula (I. C.2), wherein Y is NH, R1 is benzyl and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 144
Compounds of the formula (I. C.2), wherein Y is NCH3, R1 is benzyl and the combina- tion of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 145
Compounds of the formula (I. C.3), wherein Y is O, R1 is hydrogen, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 146
Compounds of the formula (I. C.3), wherein Y is S, R1 is hydrogen, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 147 Compounds of the formula (I. C.3), wherein Y is NH, R1 is hydrogen, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 148 Compounds of the formula (I. C.3), wherein Y is NCH3, R1 is hydrogen, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 149 Compounds of the formula (I. C.3), wherein Y is O, R1 is CH3, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4b for a compound corresponds in each case to one row of table A.
Table 150 Compounds of the formula (I. C.3), wherein Y is S, R1 is CH3, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4b for a compound corresponds in each case to one row of table A.
Table 151 Compounds of the formula (I. C.3), wherein Y is NH, R1 is CH3, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 152 Compounds of the formula (I. C.3), wherein Y is NCH3, R1 is CH3, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 153 Compounds of the formula (I. C.3), wherein Y is O, R1 is phenyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A. Table 154
Compounds of the formula (I. C.3), wherein Y is S, R1 is phenyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 155
Compounds of the formula (I. C.3), wherein Y is NH, R1 is phenyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 156
Compounds of the formula (I. C.3), wherein Y is NCH3, R1 is phenyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 157
Compounds of the formula (I. C.3), wherein Y is O, R1 is benzyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 158
Compounds of the formula (I. C.3), wherein Y is S, R1 is benzyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 159
Compounds of the formula (I. C.3), wherein Y is NH, R1 is benzyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 160
Compounds of the formula (I. C.3), wherein Y is NCH3, R1 is benzyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 161
Compounds of the formula (I. C.4), wherein Y is O, R1 is hydrogen, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 162
Compounds of the formula (I. C.4), wherein Y is S, R1 is hydrogen, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 163
Compounds of the formula (I. C.4), wherein Y is NH, R1 is hydrogen, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 164
Compounds of the formula (I. C.4), wherein Y is NCH3, R1 is hydrogen, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 165
Compounds of the formula (I. C.4), wherein Y is O, R1 is CH3, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4b for a compound corresponds in each case to one row of table A.
Table 166
Compounds of the formula (I. C.4), wherein Y is S, R1 is CH3, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4b for a compound corresponds in each case to one row of table A.
Table 167
Compounds of the formula (I. C.4), wherein Y is NH, R1 is CH3, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 168
Compounds of the formula (I. C.4), wherein Y is NCH3, R1 is CH3, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 169
Compounds of the formula (I. C.4), wherein Y is O, R1 is phenyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 170 Compounds of the formula (I. C.4), wherein Y is S, R1 is phenyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 171 Compounds of the formula (I. C.4), wherein Y is NH, R1 is phenyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 172 Compounds of the formula (I. C.4), wherein Y is NCH3, R1 is phenyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 173 Compounds of the formula (I. C.4), wherein Y is O, R1 is benzyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 174 Compounds of the formula (I. C.4), wherein Y is S, R1 is benzyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 175 Compounds of the formula (I. C.4), wherein Y is NH, R1 is benzyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table 176 Compounds of the formula (I. C.4), wherein Y is NCH3, R1 is benzyl, RT3 has in each case one of the meanings given in one row of table B and the combination of (Rz1)n, R4a and R4bfor a compound corresponds in each case to one row of table A.
Table A:
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Table B
Figure imgf000060_0002
Figure imgf000060_0003
Figure imgf000061_0001
Figure imgf000061_0002
Figure imgf000062_0002
Figure imgf000062_0003
The compounds of formula (I) can be obtained as outlined in schemes 1 to 14.
In the following, compounds (I) wherein Z is a group (I I. A) are named compounds (I .A), compounds (I) wherein Z is a group (II. B) are named compounds (I. B) and compounds (I) wherein Z is a group (II. C) are named compounds (I. C).
The compounds of the formula (I. A) according to the invention wherein X is oxygen or sulphur and R2a is hydrogen (referred herein as compounds I.A.a) can be prepared e.g. from the corresponding urea compounds IV and thiourea compounds III, respectively, as shown in scheme 1.
Scheme 1
Figure imgf000062_0001
(MI) X = S (IAa) (IV) X = O
The variables R1, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, RZ1, m and n have the meanings given above.
The thiourea compound (III) and the urea compound (IV), respectively, can be cyclized by conventional means thereby obtaining the azoline compound of the formula (I.A.a). Cyclization of the compound (III) and (IV), respectively, can be achieved e.g. under acid catalysis or under dehydrating conditions e.g. by Mitsunobu's reaction (see Tetrahedron Letters 1999, 40, 3125-3128). Alternatively, the cyclization can be carried out in the presence of a trialkyl- or tricy- cloalkylphosphine, such as trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine or tricyclohexylphosphine, a triarylphosphine, such as triphenylphosphine, or, preferably, in the presence of a phosphonium salt of the formula [P(Rα)3Rβ]+ A- wherein Rα is Ci-C4-alkyl, cyclohexyl or phenyl; Rβ is CH2-U, where U is Ci-C4-alylcarbonyl, Ci-C4-alkoxycarbonyl or, preferably, CN; and A is an anion equivalent, for example a halide anion. A particularly suited phosphorus reagent is cyanomethyltrimethylphosphonium iodide (see Tetrahedron 2001 , 57, 5451-54). Moreover, this variant is suitably carried out in the presence of a base, which is suitably an amine, such as triethylamine or diisopropylethylamine. This variant can be carried out in analogy to the method described in US 2005/0032814.
Alternatively, the compounds of the formula (I. A) according to the invention wherein X is O or S and R2a, R3a, R3b, R3c and R3d are hydrogen (referred herein as compounds (I.A.b)) can be prepared by the method shown in scheme 2.
Scheme 2
Figure imgf000063_0001
The variables R1, R4a, R4b, R4c, R4d, RZ1, m and n have the meanings given above.
An amine V or a salt thereof can be converted into an azoline (I.A.b) by reaction with 2- chloroethylisothiocyanate or 2-chloroethylisocyanate (e.g. as described in Bioorg. Med. Chem. Lett. 1994, 4, 2317-22) and subsequent cyclization in the presence or absence of a base.
1-Chloro-2-isothiocyanatoethane (CAS 6099-88-3), 2-chloroethylisocyanate (CAS 1943-83-5), 1-bromo-2-isothiocyanatoethane (CAS 1483-41-6) and 2- bromoethylisocyanate (CAS 42865-19-0) are commercially available.
This method often affords as by-product a compound (I.B.1 ):
Figure imgf000064_0001
(I.B.a)
The variables R1, R4a, R4b, R4c, R4d, RZ1, m and n have the meanings given above. X is O or S.
Compounds of the formula (I .A) according to the invention wherein X is NR5 (referred herein as compounds (I.A.c)) may be prepared by the method outlined in scheme 3.
Scheme 3
Figure imgf000064_0002
The variables R1, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, R5, RZ1, m and n have the meanings given above. LG is a leaving group, e.g. a halogen atom, a tosylate or a triflate group.
Compounds of the formula (I.A.c) may be obtained by reacting an appropriate substituted amine (V) or a salt thereof with a 2-substituted imidazoline (Vl) in an appropriate solvent. This reaction can be carried out, for example analogous to the methods described in US 5,130,441 or EP 0389765.
Amines (V) are known in the art or can be prepared by methods familiar to an organic chemist, for instance by application of general methods for the synthesis of amines. Suitable amine salts (V) are e.g. the acid addition salts formed by treating an amine (V) with an inorganic or organic acid. Anions of useful acids are e.g. sulfate, hydrogen sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, chloride, bromide, p-toluene sulfonate, and the anions of Ci-C4-alkanoic acids such as acetate, propionate, and the like. For instance, amines (V) can be prepared from suitable ketones (VII) by the methods depicted in schemes 4 and 5 below.
Scheme 4
Figure imgf000065_0001
(VII) (V.a)
The variables R4a, R4b, R4c, R4d, RZ1, m and n have the meanings given above.
Amines (V) wherein R1 is hydrogen (V.a) can be obtained through reductive amination using e. g. NH4OAc and NaCNBHs or NH2θH/ZnOAc (see R. C. Larock, Comprehensive Organic Transformations 2nd Ed., Wiley-VCH, 1999, p. 843-846). Alternatively, compounds (V.a) can be prepared by reduction of the ketone and subsequent amination of the resulting alcohol (see Mitsunobu, Hughes, Organic Reactions 1992, 42, 335-656).
Scheme 5
Figure imgf000065_0002
(VII) (VIM) (V)
The variables R1, R4a, R4b, R4c, R4d, RZ1, m and n have the meanings given above. Met is a metalorganic residue, such as Mg-HaI (Hal = halogen), Li, Zn-R (R = alkyl) or SnRβ (R = alkyl), t-Bu is tert-butyl and R is d-Ce-alkyl.
Amines (V) wherein R1 is different from hydrogen (V. b) can be obtained from the ketone (VII) via a two step synthesis. In a first step the ketone is reacted with a suitable sulfinamide such as (2-methyl-2-propane)sulfinamide in presence of a Lewis acid such as titanium tetraalkylate, e.g. titanium tetraisopropylate or titanium tetraethyl. The radical R1 is subsequently introduced via a nucleophilic addition of a metallorganic compound R1-Met followed by protonation and deprotection of the amino group. Suitable ketones (VII) are known in the art or can be prepared by methods familiar to an organic chemist, for instance by application of general methods for the synthesis of ketones, lndanone (ketone (VII) wherein m is 1 , n is 0 and R4a, R4a, R4a, and R4a are H) and β-tetralon (ketone (VII) wherein m is 2, n is 0 and R4a, R4a, R4a, and R4a are H) are commercially available. Schemes 6 and 7 below illustrate some synthetic routes towards substituted ketones (VII).
Scheme 6
Figure imgf000066_0001
(IX) (Vll.a)
The variables RZ1, m and n have the meanings given above.
Ketones (Vll.a) wherein R4a, R4b, R4c and R4d are hydrogen can be prepared by epoxidation of an indene ((IX); m = 1) or a dihydronaphthalene ((IX); m = 2), acidic cleavage of the epoxide followed by elimination of water and tautomerization of the enol. Epoxidation and subsequent cleavage and water elimination can be carried out by standard procedures as described, for example, in J. March, Advanced Organic Chemistry, Wiley. Suitable epoxidation reagents are for example peracids, such as perfumaric acid, peracetic acid, perbenzoic acid and m-chloroperbenzoic acid.
Scheme 7
Figure imgf000066_0002
(Vll.a) (VII)
Ketones (VII) wherein at least one of the radicals R4a, R4b, R4c and R4d is different from hydrogen (if R4c and/or R4d are different from hydrogen, they are directly neighboured to the carbonyl group in case m is 2) can be obtained from a suitable α-unsubstituted ketone (Vll.a) via alkylation or palladium-catalyzed arylation (see M. Palucki, S. L. Buchwald J. Am. Chem. Soc. 1997, 1 19, 1 1108-.11 109 or J. M. Fox, X. Huang, A. Chieffi, S. L. Buchwald J. Am. Chem. Soc. 2000, 122, 1360-1370) of the enolate species.
Alternatively, α-substituted ketones (VII) can be obtained from an intramolecular Friedel-Crafts-Acylation of a suitable aromatic acid chloride (see Y. Oshiro et al. J. Med. Chem. 1991 , 34, 2004-2013 or W. Vaccaro et al. J. Med. Chem. 1996, 39, 1704- 1719).
Compounds of the formula (I .A) and (I. B) wherein R2a and R2b are different from hydro- gen can be obtained as outlined in scheme 8.
Scheme 8
Figure imgf000067_0001
Figure imgf000067_0002
The variables X, RZ1, R1, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, m and n are as defined above. LG is a leaving group, e.g. a halide ion, such as Cl or Br, a tosylate or a triflate group.
A compound (I.A.b) wherein R2a and R2b, respectively, are hydrogen is treated with a suitable electrophile. Suitable electrophiles are e.g. alkylating or acylating agents R2a,2b.|_(3 (LQ = |eaving group) e.g. as described in WO 2005/063724.
Compounds of the formula (III) and (IV), respectively, can be prepared as shown in schemes 9 and 10 below.
Scheme 9
Figure imgf000068_0001
(V) (X) (Xl) (IM) X = S (IV) X = O
The variables RZ1, R1, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, m and n are as defined above. X is O or S.
An amine (V) or a salt thereof is converted to the corresponding iso(thio)cyanate (X) by conventional means, e.g. by reacting (V) with (thio)phosgene, as described for example in the case of thiophosgene in Houben-Weyl, E4, "Methoden der Organischen Che- mie", chapter Nc, pp. 837-842, Georg Thieme Verlag 1983. It may be advantageous to carry out the reaction in the presence of a base. The iso(thio)cyanate (X) is then reacted with an aminoethanol (Xl) to form an amino(thio)carbonylaminoethane compound. The reaction of the aminoethanol (Xl) with iso(thio)cyanate (X) can be performed in accordance with standard methods of organic chemistry, see e.g. Biosci. Biotech. Biochem. 56 (7), 1062-65 (1992).
Another method for preparing compounds of formula (III) wherein X is S is shown in scheme 10.
Scheme 10
Figure imgf000068_0002
(V) (XII) (III)
The variables RZ1, R1, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, m and n are as defined above.
An amine (V) or a salt thereof can be converted to the corresponding thiourea compound (III) by reaction of the amine (V) with an isothiocyanate (XII) and subsequent saponification (see G. Liu et al. J. Org. Chem. 1999, 64, 1278-1284). lsothiocyanates of formula (XII) can be prepared according to the procedures described in Coll. Czech. Chem. Commun. 1986, 51 , 1 12-117. Compounds III and IV belong to the group of compounds (I. C). They can be converted into compounds (I. C) wherein T is ORT1 with RT1 being different from hydrogen by standard etherification procedures, e.g. by reaction with an alkyl, alkenyl, alkynyl, aryl etc. halide RT1-Hal (Hal = halide). Compounds (I.C) wherein T is ORT1 with RT1 being different from hydrogen can also be prepared in analogy to the syntheses outlined in schemes 9 and 10 by using instead of the alcohols (Xl) or (XII) the etherified compounds (NH2-C(R3cR3d)-C(R3cR3d)-ORT1 and S=C=N-C(R3cR3d)-C(R3cR3d)-ORT1, respectively.
Compounds (I.C) wherein T is SRT2 can also be prepared in analogy to the syntheses outlined in schemes 9 and 10 by using instead of the alcohols (Xl) or (XII) the corresponding thiols (NH2-C(R3cR3d)-C(R3cR3d)-SH and S=C=N-C(R3cR3d)-C(R3cR3d)-SH, respectively) or the corresponding thioethers (NH2-C(R3cR3d)-C(R3cR3d)-SRT2 and S=C=N-C(R3cR3d)-C(R3cR3d)-SRT2, respectively).
Compounds (III) and (IV) can also be converted into compounds (I.C) wherein T is -0-C(O)-R1"3 or -0-C(S)-R1"4 by esterification with the corresponding (thio)acid chloride CI-C(V)-R1", wherein V is O or S and R1 is R1"3 if V is O and R1"4 if V is S, as outlined below in scheme 11. X corresponds here to Y in the general formula (I.C).
Scheme 1 1
Figure imgf000069_0001
(IM) X = S (I.C.a) (IV) X = O
The variables RZ1, R1, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, m and n are as defined above. X is O or S, V is O or S, R1 is R1"3 if V is O and R1"4 if V is S.
The reaction is generally carried out in the presence of a base such as an amine. The (thio)acid chlorides are either commercially available or can be prepared from the corresponding acids or esters by chlorination e.g. with thionylchloride. The corresponding acids and esters can be prepared by standard procedures.
Compounds (I.C) wherein Y is O or S and T is -O-C(O)-RT3, -0-C(S)-R14 or S-C(S)-R15 can also be prepared starting from an amine (V) and an iso(thio)cyanate (XIII) as shown in scheme 12. Scheme 12
Figure imgf000070_0001
(V) (XIII) (I.C.b)
The variables RZ1, R1, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, m and n are as defined above. Y is O or S, V is O or S, R1 is RT3 if V and W are both O, R1 is RT4 if V is S and W is O, and R1 is RT5 if V and W are both S.
An amine (V) or a salt thereof can be converted to the corresponding (thio)urea com- pound (I.C.b) by reaction of the amine (V) with an iso(thio)cyanate (XIII) (see G. Liu et al. J. Org. Chem. 1999, 64, 1278-1284). lsothiocyanates of formula (XIII) can be prepared according to the procedures described in Coll. Czech. Chem. Commun. 1986, 51 , 112-117.
Compounds of formula (I. C) wherein Y is NH can be synthesized in analogy to the method described in scheme 9, however using in the first step guanidine dichloride (CbC=NH) instead of (thio)phosgene.
Alternatively, compounds of formula (I. C) wherein Y is NH can be synthesized as out- lined in scheme 13 by reacting an amine (V) with the guanidine derivative (XIV):
Scheme 13
Figure imgf000070_0002
(V) (XIV) (I.C.c)
The variables RZ1, R1, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, m and n are as defined above. LG is Cl, imidazolyl or pyrazolyl. Compounds of formula (I. C) wherein Y is NH can also be synthesized as outlined in scheme 14 by reacting an amine (V) with the guanidine derivative (XV) and subsequent alkylation of the Nhb group:
Scheme 14
Figure imgf000071_0001
Figure imgf000071_0002
(I.C.d)
The variables RZ1, R1, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, m and n are as defined above. LG1 is Cl, imidazolyl or pyrazolyl. LG1 is a leaving group such as Cl, Br, a tosy- late or a triflate group.
In a first step, an amine (V) is reacted with guanidine chloride or with imidazol or pyra- zolamidine (XV) to the guanidine (XVI) which is then alkylated to give the compound (I.C.d). The alkylation can additionally take place at the NH groups of (XVI), thus providing compounds (I. C) wherein R2c and/or R2d and/or R5a are a group -C(R3cR3d)-C(R3aR3b)-T.
As a rule, the compounds of the formula (I) can be prepared by the methods described above. If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds (I) or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds (I) can advantageously be prepared from other compounds (I) by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel. Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or digestion.
Due to their excellent activity, the compounds of the general formula (I) may be used for controlling animal pests.
Accordingly, the present invention also provides a method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a plant, seed, soil, area, material or environment in which the pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of the formula I or a salt thereof or a composition as defined above.
Preferably, the method of the invention serves for protecting seed and the plant which grows therefrom from animal pest attack or infestation and comprises treating the seed with a pesticidally effective amount of a compound of the formula I or an agriculturally acceptable salt thereof as defined above or with a pesticidally effective amount of an agricultural composition as defined above and below. The method of the invention is not limited to the protection of the "substrate" (plant, seed, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated seed, the plant itself not having been treated.
In the sense of the present incention, "animal pests" are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes.
The invention further provides an agricultural composition for combating such animal pests, which comprises such an amount of at least one compound of the general formula (I) or at least one agriculturally useful salt thereof and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.
Such a composition may contain a single active compound of the formula (I) or a salt thereof or a mixture of several active compounds (I) or their salts according to the present invention. The composition according to the present invention may comprise an individual isomer or mixtures of isomers as well as individual tautomers or mixtures of tautomers. The compounds of the formula (I) and the pestidicidal compositions comprising them are effective agents for controlling arthropod pests and nematodes. Animal pests controlled by the compounds of formula (I) include for example
Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb- dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol- letis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseu- dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frus- trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis;
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12- punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hip- pocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhyn- chus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyl- lopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria;
dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicu- laris, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hyso- cyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa;
thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci;
hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta;
heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor;
homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactu- cae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus as- calonicus, Myzus cerasi, Myzus persicae, Myzus varians, Nasonovia ribis-nigri, NiIa- parvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosi- phum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Sogatella furcifera Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii;
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes flavipes, Reticulitermes lucifugus und Termes natalensis;
orthopterans (Orthoptera), e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melano- plus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus;
Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis;
Siphonatera, e.g. Xenopsylla cheopsis, Ceratophyllus spp ;
The compositions and compounds of formula (I) are useful for the control of nema- todes, especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla,Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species;
cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Het- erodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; AwI nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nema- todes, Longidorus elongatus and other Longidorus species; Pin nematodes, Paratylen- chus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species,
Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhyn- chus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus spe- cies; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.
In a preferred embodiment of the invention the compounds of formula (I) are used for controlling insects or arachnids, in particular insects of the orders Lepidoptera, Coleop- tera, Thysanoptera and Homoptera and arachnids of the order Acarina. The compounds of the formula (I) according to the present invention are particularly useful for controlling insects of the order Thysanoptera and Homoptera.
The compounds of formula (I) or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pesticidally effective amount of compounds of formula (I). The term "crop" refers both to growing and harvested crops.
The compounds of formula (I) can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
The formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961 , Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001 , 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, anti- foaming agents, anti-freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
Examples of suitable solvents are water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (N-methyl-pyrrolidones [NMP], N-octyl-pyrrolidone [NOP]), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used. Suitable emulsifiers are nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).
Examples of dispersants are lignin-sulfite waste liquors and methylcellulose.
Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalene- sulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropyl- ene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, etha- nol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.
Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
A suitable preservative is e.g. dichlorophen.
Seed treatment formulations may additionally comprise binders and optionally colorants.
Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers EO/PO surfactants but also polyvinylalcoholsl, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybute- nes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, poly- ethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, ty- lose and copolymers derived from these polymers.
Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples of a gelling agent is carrageen (Satiagel®).
Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium ni- trate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound(s). In this case, the active compound(s) are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).
For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.
The compounds of formula (I) can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusta- ble products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended pur- poses; they are intended to ensure in each case the finest possible distribution of the active compound(s) according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 % per weight.
The active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.
The following are examples of formulations:
1. Products for dilution with water for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
A) Water-soluble concentrates (SL, LS)
10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolves upon dilution with water, whereby a formula- tion with 10 % (w/w) of active compound(s) is obtained.
B) Dispersible concentrates (DC)
20 parts by weight of the active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compound(s) is obtained.
C) Emulsifiable concentrates (EC)
15 parts by weight of the active compound(s) are dissolved in 7 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formulation with 15% (w/w) of active compound(s) is obtained.
D) Emulsions (EW, EO, ES)
25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.
E) Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
F) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active compound^), whereby a formulation with 50% (w/w) of active compound(s) is obtained.
G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s) , whereby a formulation with 75% (w/w) of active compound(s) is obtained.
H) Gel-Formulation (GF)
In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
2. Products to be applied undiluted for foliar applications. For seed treatment pur- poses, such products may be applied to the seed diluted or undiluted.
I) Dustable powders (DP, DS)
5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s)
J) Granules (GR, FG, GG, MG)
0.5 parts by weight of the active compound(s) is ground finely and associated with 95.5 parts by weightof carriers, whereby a formulation with 0.5% (w/w) of active compound^) is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
K) ULV solutions (UL)
10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound(s), which is applied undiluted for foliar use.
The compounds of formula (I) are also suitable for the treatment of seeds. Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having preger- minated the latter
In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Other preferred FS formulations of compounds of formula (I) for seed treatment com- prise from 0.5 to 80 wt% of the active ingredient, from 0,05 to 5 wt% of a wetter, from 0.5 to 15 wt% of a dispersing agent, from 0,1 to 5 wt% of a thickener, from 5 to 20 wt% of an anti-freeze agent, from 0,1 to 2 wt% of an anti-foam agent, from 1 to 20 wt% of a pigment and/or a dye, from 0 to 15 wt% of a sticker /adhesion agent, from 0 to 75 wt% of a filler/vehicle, and from 0,01 to 1 wt% of a preservative.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1 :10 to 10:1.
The compounds of formula (I) are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
For use against ants, termites, wasps, flies, mosquitos, crickets, or cockroaches, compounds of formula (I) are preferably used in a bait composition.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to par- ticular necessities in terms of stickyness, moisture retention or aging characteristics.
The bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
Formulations of compounds of formula (I) as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 2500C, dimethyl- formamide, N-methylpyrrolidone, dimethyl sulphoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
The compounds of formula (I) and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of formula (I) and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like, lnsecticidal compositions for application to fibers, fabric, knitgoods, nonwov- ens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are N,N-diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3- cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/-)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)- trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-i-epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets.
Methods which can be employed for treating the seed are, in principle, all suitable seed treatment and especially seed dressing techniques known in the art, such as seed coating (e.g. seed pelleting), seed dusting and seed imbibition (e.g. seed soaking). Here, "seed treatment" refers to all methods that bring seeds and the compounds of formula (I) into contact with each other, and "seed dressing" to methods of seed treatment which provide the seeds with an amount of the compounds of formula (I), i.e. which generate a seed comprising the compound of formula (I). In principle, the treatment can be applied to the seed at any time from the harvest of the seed to the sowing of the seed. The seed can be treated immediately before, or during, the planting of the seed, for example using the "planter's box" method. However, the treatment may also be carried out several weeks or months, for example up to 12 months, before planting the seed, for example in the form of a seed dressing treatment, without a substantially reduced efficacy being observed.
Expediently, the treatment is applied to unsown seed. As used herein, the term "unsown seed" is meant to include seed at any period from the harvest of the seed to the sowing of the seed in the ground for the purpose of germination and growth of the plant.
Specifically, a procedure is followed in the treatment in which the seed is mixed, in a suitable device, for example a mixing device for solid or solid/liquid mixing partners, with the desired amount of seed treatment formulations, either as such or after previous dilution with water, until the composition is distributed uniformly on the seed. If ap- propriate, this is followed by a drying step.
The compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.
An object of the present invention is therfore also to provide new methods to control parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.
The invention also relates to compositions containing a parasiticidally effective amount of compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.
The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it. The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a compound of formula (I) or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
Surprisingly, it has now been found that compounds of formula (I) are suitable for combating endo- and ectoparasites in and on animals.
Compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infestations and infections in animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
Compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
The compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are suitable for systemic and/or non- systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
The compounds of formula (I) are especially useful for combating ectoparasites.
The compounds of formula (I) are especially useful for combating parasites of the fol- lowing orders and species, respectively: fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis,
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An- astrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inor- nata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intes- tinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Lep- toconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus ar- gentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sar- cophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis,
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthi- rus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Orni- thodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Orni- thonyssus bacoti and Dermanyssus gallinae,
Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus, Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,
Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp,
Roundworms Nematoda:
Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp,
Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,
Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunosto- mum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp. , Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioc- tophyma renale,
Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi,
Camallanida, e.g. Dracunculus medinensis (guinea worm)
Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Hab- ronema spp.,
Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracantho- rhynchus hirudinaceus and Oncicola spp,
Planarians (Plathelminthes):
Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilhar- zia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp, Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.
The compounds of formula (I) and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
Moreover, the use of the formula (I) and compositions containing them for combating mosquitoes is especially preferred.
The use of the compounds of formula (I) and compositions containing them for combating flies is a further preferred embodiment of the present invention.
Furthermore, the use of the compounds of formula (I) and compositions containing them for combating fleas is especially preferred.
The use of the compounds of formula formula (I) and compositions containing them for combating ticks is a further preferred embodiment of the present invention.
The compounds of formula (I) also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
Administration can be carried out both prophylactically and therapeutically.
Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
For oral administration to warm-blooded animals, the formula (I) compounds may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the formula (I) compounds may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula (I) compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the formula (I) compounds may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The formula (I) compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the formula (I) compounds may be formulated into an implant for subcutaneous administration. In addition the formula (I) compound may be transdermally administered to animals. For parenteral administra- tion, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula (I) compound.
The formula (I) compounds may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the formula (I) compound. In addition, the formula (I) compounds may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
Suitable preparations are:
Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
Emulsions and suspensions for oral or dermal administration; semi-solid preparations;
Formulations in which the active compound is processed in an ointment base or in an oil-in-water or water-in-oil emulsion base;
Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound- containing shaped articles.
Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile.
Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.
The active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester. Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.
Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.
Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being nec- essary.
Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, me- thylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylforma- mide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment- like consistency results. The thickeners employed are the thickeners given above.
Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added.
Suitable solvents are water, alkanols, glycols, polyethylene glycols, polypropylene gly- cols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyetha- nol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as al- kylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbon- ates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N-methylpyrrolidone, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1 ,3-diox- olane and glycerol formal.
Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.
Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.
Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
Suitable light stabilizers are, for example, novantisolic acid.
Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacry- lates, natural polymers such as alginates, gelatin.
Emulsions can be administered orally, dermally or as injections.
Emulsions are either of the water-in-oil type or of the oil-in-water type.
They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.
Suitable hydrophobic phases (oils) are: liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length Cs-Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Cs-do fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof.
Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
Suitable emulsifiers are: non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monoo- leate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; cation-active surfactants, such as cetyltrimethylammonium chloride.
Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
Liquid suspending agents are all homogeneous solvents and solvent mixtures.
Suitable wetting agents (dispersants) are the emulsifiers given above.
Other auxiliaries which may be mentioned are those given above. Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
For the production of solid preparations, the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.
Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of applica- tion, and the like.
The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of formula (I).
Generally, it is favorable to apply the compounds of formula (I) in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 percent by weight, preferably from 0.1 to 65 percent by weight, more preferably from 1 to 50 percent by weight, most preferably from 5 to 40 percent by weight. Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 percent by weight, preferably of 1 to 50 percent by weight.
Furthermore, the preparations comprise the compounds of formula (I) against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 percent by weight, very particularly preferably of 0.005 to 0.25 percent by weight.
In a preferred embodiment of the present invention, the compositions comprising the compounds of formula (I) are applied dermally / topically.
In a further preferred embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally, it is favorable to apply solid formulations which release compounds of formula (I) in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose de- rivatives, polyamides and polyester which are sufficiently compatible with the compounds of formula (I). A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
Compositions to be used according to this invention may also contain other active in- gredients, for example other pesticides, insecticides, herbicides, fungicides, other pesticides, or bactericides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
These agents can be admixed with the agents used according to the invention in a weight ratio of 1 :10 to 10:1. Mixing the compounds (I) or the compositions comprising them in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action. The following list of pesticides together with which the compounds (I) can be used, is intended to illustrate the possible combinations, but not to impose any limitation:
A.1. Organo(thio)phosphates: acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos- methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicro- tophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phor- ate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirim- fos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamido- thion;
A.2. Carbamates: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxy- carboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, pro- poxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate;
A.3. Pyrethroids: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-, yfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flu- cythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, permethrin, phenothrin, prallethrin, resmethrin, RU 15525, silafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin, ZXI 8901 ;
A.4. Juvenile hormone mimics: hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;
A.5. Nicotinic receptor agonists/antagonists compounds: acetamiprid, bensultap, cartap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nico- tine, spinosad (allosteric agonist), thiacloprid, thiocyclam, thiosultap-sodium, and AKD1022.
A.6. GABA gated chloride channel antagonist compounds: chlordane, endosulfan, gamma-HCH (lindane); acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vaniliprole, the phenylpyrazole compound of formula F1
Figure imgf000096_0001
A.7. Chloride channel activators: abamectin, emamectin benzoate, milbemectin, Ie- pimectin;
A.8. METI I compounds: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufen- pyrad, tolfenpyrad, flufenerim, rotenone;
A.9. METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
A.10. Uncouplers of oxidative phosphorylation: chlorfenapyr, DNOC;
A.1 1. Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fen- butatin oxide, propargite, tetradifon;
A.12. Moulting disruptors: cyromazine, chromafenozide, halofenozide, methoxy- fenozide, tebufenozide;
A.13. Synergists: piperonyl butoxide, tribufos;
A.14. Sodium channel blocker compounds: indoxacarb, metaflumizone;
A.15. Fumigants: methyl bromide, chloropicrin sulfuryl fluoride;
A.16. Selective feeding blockers: crylotie, pymetrozine, flonicamid;
A.17. Mite growth inhibitors: clofentezine, hexythiazox, etoxazole;
A.18. Chitin synthesis inhibitors: buprofezin, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, te- flubenzuron, triflumuron;
A.19. Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
A.20. octapaminergic agonsits: amitraz; A.21. ryanodine receptor modulators: flubendiamide;
A.22. Various: aluminium phosphide, amidoflumet, benclothiaz, benzoximate, bifenazate, borax, bromopropylate, cyanide, cyenopyrafen, cyflumetofen, chinomethionate, dicofol, fluoroacetate, phosphine, pyridalyl, pyrifluquinazon, sulfur, tartar emetic;
A.23. N-R'-2,2-dihalo-1-R"cyclo-propanecarboxamide-2-(2,6-dichloro-α,α,α-tri-fluoro-p- tolyl)hydrazone or N-R'-2,2-di(R'")propionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)- hydrazone, wherein R' is methyl or ethyl, halo is chloro or bromo, R" is hydrogen or methyl and R'" is methyl or ethyl;
A.24. Anthranilamides: chloranthraniliprole, the compound of formula F2
Figure imgf000097_0001
A.25. Malononitrile compounds: CF3(CH2)2C(CN)2CH2(CF2)3CF2H, CF3(CH2)2C(CN)2CH2(CF2)5CF2H, CF3(CH2)2C(CN)2(CH2)2C(CF3)2F, CF3(CH2)2C(CN)2(CH2)2(CF2)3CF3, CF2H(CF2)SCH2C(CN)2CH2(CF2)SCF2H, CF3(CH2)ZC(CN)2CH2(CF2)SCFS, CF3(CF2)2CH2C(CN)2CH2(CF2)sCF2H, CFSCF2CH2C(CN)2CH2(CF2)SCF2H, 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4,4,4- pentafluorobutyl)-malonodinitrile, and CF2HCF2CF2CF2CH2C(CN) 2CH2CH2CF2CF3;
A.26. Microbial disruptors: Bacillus thuringiensis subsp. Israelensi, Bacillus sphaericus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;
A.27. Alkynylether compounds T4 and T5:
Figure imgf000097_0002
wherein R is methyl or ethyl and Het* is 3,3-dimethylpyrrolidin-1-yl, 3-methylpiperidin-1- yl, 3,5-dimethylpiperidin-1-yl, 3-trifluormethylpiperidin-1-yl, hexahydroazepin-1-yl, 2,6- dimethylhexahydroazepin-1-yl or 2,6-dimethylmorpholin-4-yl. These compounds are described e.g. in JP 2006131529.
The commercially available compounds of the group A may be found in The Pesticide Manual, 13th Edition, British Crop Protection Council (2003) among other publications.
Thioamides of formula r1 and their preparation have been described in WO 98/28279. Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004. Ben- clothiaz and its preparation have been described in EP-A1 454621. Methidathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Acetoprole and its preparation have been described in WO 98/28277. Metaflumizone and its preparation have been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779. Pyrafluprole and its preparation have been de- scribed in JP 2002193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in US 6335357. Amidoflumet and its preparation have been described in US 6221890 and in JP 21010907. Flufenerim and its preparation have been described in WO 03/007717 and in WO 03/007718. AKD 1022 and its preparation have been described in US 6300348. Chloranthraniliprole has been de- scribed in WO 01/70671 , WO 03/015519 and WO 05/118552. Anthranilamide derivatives of formula r2 have been described in WO 01/70671 , WO 04/067528 and WO 05/118552. Cyflumetofen and its preparation have been described in WO 04/080180. The aminoquinazolinone compound pyrifluquinazon has been described in EP A 109 7932. The malononitrile compounds CF3(CH2)2C(CN)2CH2(CF2)3CF2H, CF3(CH2)2C(CN)2CH2(CF2)5CF2H, CF3(CH2)2C(CN)2(CH2)2C(CF3)2F,
CF3(CH2)2C(CN)2(CH2)2(CF2)3CF3, CF2H(CF2)3CH2C(CN)2CH2(CF2)3CF2H, CF3(CH2)2C(CN)2CH2(CF2)3CF3, CF3(CF2)2CH2C(CN)2CH2(CF2)3CF2H, CF3CF2CH2C(CN)2CH2(CF2)SCF2H, 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4,4,4- pentafluorobutyl)-malonodinitrile, and CF2HCF2CF2CF2CH2C(CN) 2CH2CH2CF2CF3 have been described in WO 05/63694.
Fungicidal mixing partners are those selected from the group consisting of acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph, anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl, antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinicona- zole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, tebuconazole, triadimefon, triadimenol, triflumizol, triticonazole, flutriafol, dicarboximides such as iprodion, myclozolin, procymidon, vinclozolin, dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram, zineb, heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadon, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamid, thiophanate-methyl, tiadinil, tricyclazole, triforine, copper fungicides such as Bordeaux mixture, copper acetate, copper oxychloride, ba- sic copper sulfate, nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthalisopropyl, phenylpyrroles such as fenpiclonil or fludioxonil, sulfur, other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid, cymoxanil, diclomezin, diclocymet, diethofencarb, edifen- phos, ethaboxam, fenhexamid, fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenon, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamid, strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, me- tominostrobin, orysastrobin, picoxystrobin or trifloxystrobin, sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid, cinnemamides and analogs such as dimethomorph, flumetover or flumorph.
The animal pest, i.e. arthropodes and nematodes, the plant, soil or water in which the plant is growing can be contacted with the present compound(s) (I) or composition(s) containing them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant).
Moreover, animal pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formula (I). As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
The compounds of formula (I) and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities). The compounds of are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
The compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
The compounds of formula (I) may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula I. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 2O g per 100 m2.
Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2.
lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 % by weight, preferably from 0.1 to 45 % by weight, and more preferably from 1 to 25 % by weight of at least one repellent and / or insecticide. For use in bait compositions, the typical content of active ingredient is from 0.001 % by weight to 15 % by weight, desirably from 0.001 % by weight to 5 % by weight of active compound.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 % by weight, preferably from 0.01 to 50 % by weight and most preferably from 0.01 to 15 % by weight.
For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
In the treatment of seed, the application rates of the mixture are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 200 g per 100 kg of seed.
The present invention is now illustrated in further detail by the following examples.
Preparation examples
I. Compounds of the formula (I) wherein Z is a group of the formula II.A or II. B
Example 1 :
(4,5-Dihydro-thiazol-2-yl)-(7-methoxy-1 ,2,3,4-tetrahydro-naphthalen-2-yl)-amine (com- pound 1 )
To a solution of 1-(2-hydroxy-ethyl)-3-(7-methoxy-1 ,2,3,4-tetrahydronaphthalen-2-yl)- thiourea (0.28 g) and diisopropyethylamine (0.18 g) in propionitrile (15 ml.) was added cyanomethyltrimethylphosphonium iodide (0.30 g, Tetrahedron 2001 , 57, 5451-54). The reaction mixture was heated up to 90 0C for 5 h and stirring was continued overnight at room temperature. Purification by chromatography on silica gel yielded 0.11 g of the title compound.
Example 2: (8-Chloro-1 ,2,3,4-tetrahydro-naphthalen-2-yl)-(4,5-dihydro-thiazol-2-yl)-amine (compound 2a) and
(8-chloro-1 ,2,3,4-tetrahydro-naphthalen-2-yl)-(4,5,4',5'-tetrahydro-[2,3']bithiazolyl- 2'ylidene)amine (compound 2b)
A solution of 8-chloro-1 ,2,3,4-tetrahydro-naphthalen-2-ylamine (430 mg, 2.37 mmol) in diethyl ether (10 ml.) was cooled to 0 0C. Then a solution of 2- chloroethylisothiocyanate (0.23 ml_, 2.37 mmol) in diethyl ether (10 ml.) was added dropwise and the reaction mixture stirred for 3 h. After addition of aq. NaOH-solution (1 M, 4 ml.) and water (15 ml_), the phases were separated. The aq. phase was extracted with diethyl ether (3 times) and the combined organic phases washed with water (3 times) and dried over Na2SU4. Purification by flash chromatography (Siθ2, ChbCb/methanol 100:0 -> 90:10) yielded (8-chloro-1 ,2,3,4-tetrahydro-naphthalen-2-yl)- (4,5-dihydro-thiazol-2-yl)-amine (340 mg, 1.27 mmol, 54 %) and (8-chloro-1 ,2,3,4- tetrahydro-naphthalen-2-yl)-(4,5,4',5'-tetrahydro-[2,3']bithiazolyl-2'ylidene)amine (140 mg, 0.40 mmol, 17 %).
Compounds of the formula (I) (wherein R1, R3a, R3b, R3b, R3c, R3d, R4a, R4b, R4c and R4d are hydrogen) listed in table I below were prepared in an analogous manner.
Table I:
Figure imgf000102_0001
Figure imgf000102_0002
Figure imgf000103_0001
comp. = compound number m.p. = melting point r.t. = retention time (HPLC)
M+ = molecular mass of the detected cationic species
S = singulet d = doublet m = multiplet me = centered multiplet br = broad
II. Compounds of the formula (I) wherein Z is a group of the formula (I I. C)
Example 14: 1-(2-Hydroxyethyl)-3-(1 ,2,3,4-tetrahydronaphthalen-2-yl)-thiourea (compound 14)
A solution of thiophosgen (0.73 g) in chloroform (10 ml) was treated at room temperature with a solution of potassium carbonate (2.23 g) in water (15 ml_) and a solution of 1 ,2,3,4-tetrahydro-naphthalen-2-ylamine hydrochloride (1.00 g) in chloroform (25 ml_). After stirring overnight dichloromethane was added and the mixture extracted with water (3 x), the organic phase dried over sodium sulphate and the solvent evaporated under reduced pressure to yield 0.83 g of the crude isothiocyanate. The latter was dissolved in toluene (20 ml) and treated with 2-aminoethanol at reflux for 4 h. Stirring was continued overnight at room temperature. The mixture was then dissolved in ethyl ace- tate and extracted with water (3 x), the organic phase dried and evaporated in vacuo. The remainder was purified by column chromatography on silica gel to yield 1.00 g of the product, m.p. 89-91 0C.
Example 15: 2-Acetoxy-2-methyl-propionic acid 2-[3-(1 ,2,3,4-tetrahydro-naphthalen-2-yl)thioureido]- ethyl ester (compound 15 ) A solution of 1-(2-hydroxyethyl)-3-(1 ,2,3,4-tetrahydronaphthalen-2-yl)-thiourea (0.4O g) and triethylamine (0.16 g) in anhydrous tetrahydrofuran (20 mL) was treated with acetic acid 1-chlorocarbonyl-i-methylethyl ester (0.26 g) and stirred overnight. Purification by column chromatography on silica gel yielded 0.46 g of the product as a colourless oil.
Example 16:
Benzoic acid 2-[3-(7-methoxy-1 ,2,3,4-tetrahydro-naphthalen-2-yl)-thioureido]-ethyl ester (compound 16)
A solution of 7-methoxy-1 ,2,3,4-tetrahydro-naphthalen-2-ylamine (0.34 g) in toluene (10 ml) was treated with benzoic acid 2-isothiocyanato-ethyl ester (0.39 g, cf. Collect. Czech. Chem Commun. 1986, 51, 112-117), refluxed for 1 h and stirred at room tem- perautre overnight. Purification by Chromatography on silica gel yielded the product (0.32 g), m.p. 103-106 0C.
Example 17
Acetic acid 2-[3-(7-methoxy-1 ,2,3,4-tetrahydro-naphthalen-2-yl)-thioureido]-ethyl ester
(compound 17)
A solution of 7-methoxy-1 ,2,3,4-tetrahydro-naphthalen-2-ylamine (0.34 g) in toluene (10 mL) was treated with acetic acid 2-isothiocyanato-ethyl ester (0.28 g, cf. Collect. Czech. Chem Commun. 1986, 51 , 112-117), refluxed for 1 h and stirred at room temperature overnight. Purification by chromatography on silica gel yielded the product (0.45 g).
Compounds of the formula (I) (wherein R1, R2c, R2d, R3a, R3b, R3b, R3c, R3d, R4a, R4b, R4c and R4d are hydrogen and Y is sulfur) listed in table Il below were prepared in an analogous manner.
Table II:
Figure imgf000104_0001
Figure imgf000104_0002
Figure imgf000105_0001
Figure imgf000106_0001
comp.. = compound m.p. = melting point r.t. = retention time (HPLC)
(M + H)+ = molecular mass of the detected cationic species
Ph = phenyl
# is the binding site to the remainder of the molecule
S = singlet d = doublet m = multiplet me = centered multiplet br = broad
2. Biological examples
11.1 Cotton aphid (aphis gossypii), mixed life stages
The active compounds were formulated in 50:50 acetone : water and 100 ppm Kinetic® surfactant.
Cotton plants at the cotyledon stage (one plant per pot) were infested by placing a heavily infested leaf from the main colony on top of each cotyledon. The aphids were allowed to transfer to the host plant overnight, and the leaf used to transfer the aphids was removed. The cotyledons were dipped in the test solution and allowed to dry. After 5 days, mortality counts were made.
In this test, the compounds 2a, 3a, 8b, 9a, 11 , 12, 18, 22, 24, 25, 26, 27, 28, 30, 31 , 32, 33, 34, 35, 36, 39, 40, 43, 44, 45, 46, 47, 48, 49, 51 and 52 at 300 ppm showed a mortality of at least 50% in comparison with untreated controls.
11.2 Green Peach Aphid (Myzus persicae), mixed life stages
The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
Pepper plants in the 2nd leaf-pair stage (variety 'California Wonder') were infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections were removed after 24 hr. The leaves of the intact plants were dipped into gradient solutions of the test compound and allowed to dry. Test plants were maintained under fluorescent light (24 hour photoperiod) at about 250C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on check plants, was determined after 5 days. In this test, compounds 3a, 4a, 1 1 , 12, 18, 25, 26, 27, 28, 30, 31 , 32, 33, 34, 35, 36, 38, 39, 40, 43, 44, 45, 46, 47, 48, 49 and 52 at 300 ppm showed a mortality of at least 50% in comparison with untreated controls.
11.3 Cowpea Aphid (aphis craccivora)
The active compounds were formulated in 50:50 acetone:water and 0.1 % (vol/vol) Alkamuls EL 620 surfactant.
Potted cowpea beans of 7-10 days of age are inoculated with aphids 24 h before treatment by clipping a leaf infested with cowpea aphid approximately 30 individuals. The treated beans are sprayed with 5 ml of the test solution using air driven hand atomizer (Devillbis atomizer) at 25 psi, allowed to air dry and kept at 25-27°C and 50- 60% humidity for 3 days. After 72 h, mortality was assessed.
In this test, the compounds 3a, 4b, 5a, 1 1 , 12, 18, 25, 26, 29, 30, 34, 35, 38, 39, 40, 43, 44, 45 and 47 at 300 ppm showed a mortality of at least 60% in comparison with untreated controls.
II.4 Silverleaf Whitefly (bemisia argentifolii), adult
The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
Selected cotton plants were grown to the cotyledon state (one plant per pot). The cotyledons were dipped into the test solution to provide complete coverage of the foliage and placed in a well-vented area to dry. Each pot with treated seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately 3-5 day old) were introduced. The insects were colleted using an aspirator and an 0.6 cm, non-toxic Tygon® tubing (R-3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. The cups were covered with a reusable screened lid (150 micron mesh polyester screen PeCap from Tetko Inc). Test plants were maintained in the holding room at about 25 0C and 20-40% relative humid- ity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.
In this test, compounds 3a, 3b, 4a, 16, 17, 18 and 40, at 300 ppm showed a mortality of at least 50% in comparison with untreated controls.
11.5 Brown planthopper (nilaparvata lugens) The active compounds were formulated as a 20:80 acetone:water solution. Surfactant (Alkamuls EL 620) was added at the rate of 0.1 % (vol/vol).
Potted rice plants of 3-4 weeks of age are sprayed with 10 ml of the test solution using air driven hand atomizer (Devillbis atomizer) at 1.7 bar. The treated plants are allowed to dry for about 1 hour and covered with Mylar cages. The plants are inoculated with 10 adults of the specie (5 male and 5 females) and kept at 25-27°C and 50-60% humidity for 3 days. Mortality is assed after 24, 48 and 72 hours after treatment. Dead insects are usually found in the water surface. Each treatment is replicated once.
In this test, compounds 4b, 12, 17 and 19 at 300 ppm showed a mortality of at least 50% in comparison with untreated controls.
11.6 Southern Armyworm (spodoptera eridania), 2nd-3rd instar larvae
The active compounds were formulated as a 10.000 ppm solution in a mixture of 35% acetone and water, which was diluted with water, if needed.
A Sieva lima bean leaf expanded to 7-8 cm in length is dipped in the test solution with agitation for 3 seconds and allowed to dry in a hood. The leaf is then placed in a 100 x 10 mm petri dish containing a damp filter paper on the bottom and ten 2nd instar caterpillars. At 4 days, observations are made of mortality, reduced feeding, or any interference with normal molting.
In this test, compounds 4a, 4b, 23, 32 and 49 at 300 ppm showed a mortality of at least 50% in comparison with untreated controls.
11.7 Activity against Vetch aphid (Megoura viciae)
The active compounds were formulated in DMSO : water (1 : 3). Bean leaf disks were placed into microtiterplates filled with 0.8% agar-agar and 2.5 ppm OPUS™. The leaf disks were sprayed with 2.5 μl of the test solution and 5 to 8 adult aphids were placed into the microtiterplates which were then closed and kept at 22-24°C and 35 - 45% un- der fluorescent light for 6 days. Mortality was assessed on the basis of vital, reproduced aphids. Tests were replicated 2 times.
In this test, the compounds 8a, 9a, 9b, 18, 33, 39, 45, 47, 49 and 53 at a concentration of the test solution of 2500 mg/L showed a mortality of at least 50%.
11.8 Activity against Boll weevil (Anthonomus grandis) The active compounds were formulated in DMSO : water (1 : 3). 10 to 15 eggs were placed into microtiterplates filled with 2% agar-agar in water and 300 ppm formaline. The eggs were sprayed with 20 μl of the test solution, the plates were sealed with pierced foils and kept at 24-26°C and 75-85 % humidity with a day/night cycle for 3 to 5 days. Mortality was assessed on the basis of the remaining unhatched eggs or larvae on the agar surface and/or quantity and depth of the digging channels caused by the hatched larvae. Tests were replicated 2 times.
In this test, the compounds 4a, 5a, 25 and 40, at a concentration of the test solution of 2500 mg/L showed a mortality of at least 50%.
11.9 Activity against Mediterranean fruitfly (Ceratitis capitata)
The active compounds were formulated in 1 :3 Dimethylsulfoxide / water. 50 to 80 eggs were placed into microtiterplates filled with 0.5% agar-agar and 14 % diet in water. The eggs were sprayed with 5 μl of the test solution, the plates were sealed with pierced foils and kept at 27-290C and 75-85% humidity under fluorescent light for 6 days. Mortality was assessed on the basis of the agility of the hatched larvae. Tests were replicated 2 times.
In this test the eggs which have been treated with 2500 ppm of the active compound 18 showed a mortality of at least 50%.

Claims

Claims:
1. The use of compounds of formula (I) or of a salt thereof for combating animal pests
Figure imgf000111_0001
(I) wherein
Z is a group of the formulae (I I. A), (II. B) or (II. C)
#-
Figure imgf000111_0002
(II.A) (II. B) (M C) n is 0, 1 , 2, 3 or 4;
m is 1 or 2;
# is the binding site to the remainder of the molecule;
X is S, O or NR5;
Y is S, O or NR5a;
T is -ORT1, -SRT2, -O-C(O)-RT3, -O-C(S)-RT4 or -S-C(S)-R15;
RT1, RT2, RT3, RT4 and RT5 are selected from hydrogen,
Ci-Cβ-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, where the three last-mentioned radicals may carry 1 , 2 or 3 substituents RTa;
C3-C6-cycloalkyl which may carry 1 , 2 or 3 substituents RTb;
phenyl which may carry 1 , 2 or 3 substituents RTc; where the phenyl ring may also be fused to another phenyl ring or to a 5- or 6-membered satu- rated, partially unsaturated or aromatic 5- or 6-membered heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N and optionally 1 or 2 carbonyl groups as ring members, where the fused ring system may carry 1 , 2 or 3 substituents RTc;
saturated, partially unsaturated or aromatic 5- or 6-membered heterocyclyl containing 1 , 2 or 3 heteroatoms selected from O, S and N and optionally 1 or 2 carbonyl groups as ring members, which may carry 1 , 2 or 3 substituents RTd; or
RT3, RT4 and RT5 are NRT31RT32, where RT31 and RT32, independently of each other, are selected from hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, where the 3 last-mentioned groups may carry 1 , 2 or 3 substituents RTa, C3-C6-cycloalkyl, which may carry 1 , 2 or 3 substituents RTb; aryl and aryl-Ci-C4-alkyl, where the aryl moiety in the 2 last-mentioned groups may carry 1 , 2 or 3 substituents RTc; or
RT31 and RT32 together with the nitrogen atom to which they are bound form a 3-, 4-, 5- or 6-membered saturated, partially unsaturated or aromatic bered heterocyclic containing 1 , 2 or 3 heteroatoms selected from O, S and
N and optionally 1 or 2 carbonyl groups as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents RTd;
R1 is selected from the group consisting of hydrogen, cyano, Ci-Cβ-alkyl, Ci- Cβ-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ- alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynylcarbonyl;
C3-C6-cycloalkyl, phenyl, benzyl, phenoxycarbonyl, 5- or 6-membered hetaryl and 5- or 6-membered hetarylmethyl each of the six last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or
5 radicals Rb1;
R2a, R2b are selected from the group consisting of hydrogen, formyl, CN, Ci-Cβ- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, d-Cβ-alkylcarbonyl, C2-C6- alkenylcarbonyl, C2-C6-alkynylcarbonyl, Ci-Cβ-alkoxycarbonyl, (Ci-Cβ- alkyl)thiocarbonyl, (Ci-C6-alkoxy)thiocarbonyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals Ra2,
C(O)NRaRb, C(S)NRaRb, (SO2)NRaRb, phenyl, benzoyl, phenoxycarbonyl, benzyl, benzylcarbonyl, benzyloxycar- bonyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring, 5- or 6-membered hetarylmethyl, 5- or 6-membered hetaryl- carbonyl, 5- or 6-membered hetarylmethylcarbonyl, wherein each of the 10 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb2, and wherein the 5- or 6-membered het- eroaromatic ring in hetarylmethyl, hetarylcarbonyl and hetarylmethylcarbonyl contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, and wherein the 5- or 6-membered heterocyclic ring contains 1 , 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring members; or
R1 together with R2a may be C3-Cs-alkandiyl which may carry 1 , 2, 3, 4 or 5 radicals R21 and where one or two methylene groups of the C3-Cs-alkandiyl radical may be replaced by 1 or 2 non-adjacent heteroatoms or heteroa- tom-containing groups selected from O, S and NR22;
R1 together with R2b may also be a bridging carbonyl group C(O);
R2c and R2d, independently of each other, are selected from hydrogen, formyl, Ci-
Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, aryl, aryl-Ci-C4-alkyl, hetaryl, hetaryl- Ci-C4-alkyl, C-i-Cβ-alkylcarbonyl, C-i-Cβ-alkylthiocarbonyl, C2-C6- alkenylcarbonyl, C2-C6-alkynylcarbonyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ- alkoxythiocarbonyl, arylcarbonyl, hetarylcarbonyl, aryloxycarbonyl and hetaryloxycarbonyl, where the aliphatic, aromatic or heteroaromatic moieties in the 17 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 radicals Rc2, and where hetaryl is a 5- or 6-membered heteroaromatic ring containing 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members;
R3a, R3b, R3c, R3d, independently of each other, are selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, Ci- Cβ-haloalkyl, d-Cε-alkyl, Ci-Cε-alkylamino, di-(Ci-C6-alkyl)amino, Ci-Cβ- alkoxy, wherein the carbon atoms in the last 4 mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals Ra3,
C3-C6-cycloalkyl, phenyl or benzyl, each of the last three mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb3;
R4a, R4b, independently of each other, are selected from the group consisting of hydrogen, halogen, C-i-Cε-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Cβ- haloalkyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals Ra4,
phenyl, benzyl, 5 or 6 membered hetaryl and 5 or 6 membered hetaryl- methyl, each of the four last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb4, and wherein the 5 or 6 membered heteroaromatic ring in hetarylmethyl and hetaryl contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members; or
R4a together with R4b may also be =0, =NRC or =CRdRe; or
R4a together with R4b may also be C2-C5-alkandiyl which may carry 1 , 2, 3, 4, 5 or
6 substituents R41 and where one or two methylene groups of the C2-Cs- alkandiyl radical may be replaced by 1 or 2 non-adjacent heteroatoms or heteroatom-containing groups selected from O, S and NR42; or
R2a together with R4a may form a bridging bivalent radical selected from the group consisting of C(O)-C(R24a)(R24b), C(S)-C(R24a)(R24b), CH2-C(R24a)(R24b), S(O)2-C(R24a)(R24b), S(O)-C(R24a)(R24b), C(O)-O, C(S)-O, S(O)2-O, S(O)-O,
C(O)-NH, C(S)-NH, S(O)2-NH, S(O)-NH;
R4c, R4d are independently defined like R4a and R4b;
R5, R5a, independently of each other, are selected from the group consisting of hydrogen, formyl, CN, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C-i-Cβ- alkylcarbonyl,
Figure imgf000114_0001
C-i-Cβ- alkoxycarbonyl, Ci-Cβ-alkylthiocarbonyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals Ra5,
C(O)NRaRb, (SO2)NRaRb, C(S)NRaRb
phenyl, benzyl, phenoxycarbonyl, 5 or 6 membered hetarylmethyl, 5 or 6 membered hetarylcarbonyl and benzoyl each of the last six mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rb5, and wherein the 5 or 6 membered heteroaromatic ring in hetarylmethyl and hetarylcarbonyl contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members;
each RZ1 is independently selected from the group consisting of halogen, OH, SH, SO3H, COOH, cyano, nitro, d-Ce-alkyl, d-Ce-alkoxy, d-Ce-alkylthio, C2- Cβ-alkenyl, C2-C6-alkenyloxy, C2-C6-alkenylthio, C2-C6-alkynyl, C2-C6- alkynyloxy, C2-C6-alkynylthio, Ci-Cβ-alkylsulfonyl, Ci-Cβ-alkylsulfoxyl, C2- Cβ-alkenylsulfonyl, C2-C6-alkynylsulfonyl, a radical NRaRb, formyl, Ci-Cβ- alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynylcarbonyl, Ci-Cβ- alkoxycarbonyl, C2-C6-alkenyloxycarbonyl, C2-C6-alkynyloxycarbonyl, for- myloxy, Ci-Cβ-alkylcarbonyloxy, C2-C6-alkenylcarbonyloxy, C2-C6- alkynylcarbonyloxy, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2, 3, 4 or 5 radicals Raz,
C(O)NRaRb, (SO2)NRaRb, and radicals of the formula L-Cy, wherein
L is a single bond, oxygen, sulfur or Ci-Cβ-alkandiyl, wherein one carbon might be replaced by oxygen,
Cy is selected from the group consisting of C3-Ci2-cycloalkyl, which is unsub- stituted or substituted with any combination of 1 , 2, 3, 4 or 5 radicals Rbz, phenyl, naphthyl and mono- or bicyclic 5- to 10-membered heterocyclyl, which contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, wherein Cy is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rbz;
and wherein two radicals RZ1 that are bound to adjacent carbon atoms may form together with said carbon atoms a fused benzene ring, a fused satu- rated or partially unsaturated 5, 6, or 7 membered carbocycle or a fused 5,
6, or 7 membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals Rbz;
Ra, Rb are independently of each other selected from the group consisting of hydrogen, Ci-Cβ-alkyl, phenyl, benzyl, 5 or 6 membered hetaryl, C2-C6- alkenyl, or C2-C6-alkynyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals Raw;
Rc has one of the meanings given for Ra and Rb or is selected from the group consisting of Ci-Cβ-alkoxy, OH, NH2, Ci-Cβ-alkylamino, di(Ci-C6- alkyl)amino, arylamino, N-(Ci-C6-alkyl)-N-arylamino and diarylamino, wherein aryl is phenyl which may be unsubstituted or may carry 1 , 2 or 3 substituents Rbc; Rd, Re have one of the meanings given for Ra and Rb or are independently of each other selected from Ci-Cβ-alkoxy or di(Ci-C6-alkyl)amino.
Ra2, Ra3, Ra4, Ra5, Raw and Raz are independently of each other selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, car- boxyl, C3-C6-cycloalkyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ-haloalkoxy, Ci-Cβ-alkylcarbonyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ- alkylthio, Ci-C6-haloalkylthio, Ci-Cβ-alkylsulfonyl and Ci-Cβ- haloalkylsulfonyl;
Rb1, Rb2, Rb3, Rb4, Rb5, Rbc, Rbz and Rc2 are independently of each other selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-Cε-alkyl, d-Cε-haloalkyl, Cs-Cβ-cycloalkyl, Ci-Cβ- alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy, Ci-Cβ- alkylthio, Ci-Cε-alkylamino, di(Ci-C6-alkyl)amino, Ci-Cβ-alkylsulfonyl, Ci-Cβ- alkylsulfoxyl, formyl, Ci-Cβ-alkylcarbonyl, Ci-Cβ-alkoxycarbonyl, formyloxy, and Ci-Cβ-alkylcarbonyloxy;
R21, R24a, R24b and R41 have independently one of the meanings given for Rb1 or two radicals R21 bound to the same carbon atom may together with this carbon atom form a carbonyl group or two radicals R41 bound to the same carbon atom may together with this carbon atom form a carbonyl group;
R22, R42 independently are hydrogen, d-Cε-alkyl, C2-C6-alkenyl, C-i-Cβ-alkynyl, where the 3 last-mentioned groups may carry 1 , 2 or 3 substituents Ra42,
C3-C6-cycloalkyl, which may carry 1 , 2 or 3 substituents Rb42; aryl and aryl- Ci-C4-alkyl, where aryl moiety in the 2 last-mentioned groups may carry 1 , 2 or 3 substituents Rc42;
each RTa is independently selected from the group consisting of halogen, C3-C6- cycloalkyl, Cs-Cβ-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, Ci-C4-haloalkylcarbonyloxy, phenyl, phenyloxy, phenylthio and 5- or 6- membered hetaryl, where the phenyl moiety and the hetaryl ring in the four last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyloxy and C1-C4- haloalkylcarbonyloxy;
each RTb is independently selected from the group consisting of halogen, C1-C4- alkyl, Ci-C4-haloalkyl, Cs-Cβ-cycloalkyl, Cs-Cβ-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Cs-Cβ-cycloalkoxy, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, C1-C4- haloalkoxycarbonyl, Ci-C4-alkylcarbonyloxy, d^-haloalkylcarbonyloxy, phenyl, phenyloxy, phenylthio and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the four last-mentioned substituents may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkylcarbonyloxy and Ci-C4-haloalkylcarbonyloxy;
each RTc is independently selected from the group consisting of halogen, C1-C4- alkyl, Ci-C4-haloalkyl, Cs-Cβ-cycloalkyl, Cs-Cβ-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl,
Ci-C4-haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl,
Figure imgf000117_0001
phenyl, phenyloxy, phenylthio and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the four last-mentioned substituents may carry 1 , 2 or 3 sub- stituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkylcarbonyloxy and Ci-C4-haloalkylcarbonyloxy;
each RTd is independently selected from the group consisting of halogen, C1-C4- alkyl, Ci-C4-haloalkyl, Cs-Cβ-cycloalkyl, Cs-Cβ-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl,
Ci-C4-haloalkylcarbonyl, Ci-C4-alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl, d^-alkylcarbonyloxy, d-d-haloalkylcarbonyloxy, phenyl, phenyloxy, phenylthio and 5- or 6-membered hetaryl, where the phenyl moiety and the hetaryl ring in the four last-mentioned substituents may carry 1 , 2 or 3 sub- stituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkylcarbonyloxy and Ci-C4-haloalkylcarbonyloxy;
Ra42 is independently defined like RTa;
Rb42 is independently defined like RTb; and
Rc42 is independently defined like RTc.
2. The use as claimed in claim 1 , where RZ1 is selected from halogen, OH, SH, Ci- Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkoxy and
Ci-Cβ-haloalkoxy.
3. The use as claimed in any of the preceding claims, where n is 0 or 1.
4. The use as claimed in any of claims 1 or 2, where n is 2.
5. The use as claimed in any of the preceding claims, where R1 is hydrogen.
6. The use as claimed in any of claims 1 to 4, where R1 is d-Cε-alkyl, phenyl or benzyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 radicals Rb1.
7. The use as claimed in any of the preceding claims, where R4a, R4b, R4c and R4d are independently selected from hydrogen, C-i-Cε-alkyl, C-i-Cε-haloalkyl, phenyl or benzyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 radicals Rb4.
8. The use as claimed in any of the preceding claims, where Z is a group of the formula (II.A) or (II. B).
9. The use as claimed in claim 8, where R2a and R2b are independently selected from hydrogen, C-i-Cε-alkyl, formyl, CN, C-i-Cβ-alkylcarbonyl, Ci-Cβ- haloalkylcarbonyl, C-i-Cβ-alkoxycarbonyl, C-i^-alkoxy-d^-alkoxycarbonyl, Ci- Cβ-alkylthiocarbonyl, phenyl, benzoyl, benzyl, benzylcarbonyl, a 5- or 6- membered saturated, partially unsaturated or aromatic heterocyclic ring contain- ing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, hetaryl- methyl, hetarylcarbonyl and hetarylmethylcarbonyl, wherein each of the 8 last mentioned radicals may be unsubstituted or may carry any combination of 1 , 2 or 3 radicals Rb2, and wherein the heteroaromatic ring in hetarylmethyl, hetarylcarbonyl and hetarylmethylcarbonyl is 5- or 6-membered and contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members.
10. The use as claimed in claim 9, where R2b is selected from a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, where the heterocyclic ring may carry 1 , 2 or 3 radicals Rb2.
1 1. The use as claimed in claim 10, where R2b is selected from pyrazolinyl, imida- zolinyl, oxazolinyl and thiazolinyl.
12. The use as claimed in any of the preceding claims, where R3a, R3b, R3c and R3d are hydrogen.
13. The use as claimed in any of the preceding claims, where X is O.
14. The use as claimed in any of claims 1 to 12, where X is S.
15. The use as claimed in any of claims 1 to 12, where X is NR5.
16. The use as claimed in any of claims 1 to 7, where Z is a group of the formula (H-C).
17. The use as claimed in claim 16, where Y is S.
18. The use as claimed in any of claims 16 or 17, where R2c and R2d are hydrogen.
19. The use as claimed in any of claims 16 to 18, where T is -ORT1 or -0-C(O)-R1"3.
20. The use as claimed in claim 19, where RT1 is hydrogen.
21. The use as claimed in claim 19, where RT3 is selected from d-Cε-alkyl which may carry 1 , 2 or 3 substituents RTa, phenyl which may carry 1 , 2 or 3 substitu- ents RTc and 5- or 6-membered hetaryl containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members which may carry 1 , 2 or 3 substituents RTd.
22. The use as claimed in any of the preceding claims, for combating arthropod pests and/or nematodes.
23. The use as claimed in claim 22, for combating insects.
24. The use as claimed in claim 23, for combating insects of the order Homoptera.
25. The use as claimed in claim 23, for combating insects of the order Thysanoptera.
26. The use as claimed in claim 22, for combating acaridae.
27. An agricultural composition containing at least one compound of the formula (I) as defined in any of claims 1 to 21 and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
28. A method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a plant, seed, soil, area, material or environment in which the pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of the formula I or a salt thereof as defined in any of claims 1 to 21 or with a pesticidally ef- fective amount of an agricultural composition as defined in claim 27.
29. The method as claimed in claim 28, for protecting seed and/or the plants which grow therefrom, which method comprises treating the seed with a pesticidally effective amount of a compound of the formula I or an agriculturally acceptable salt thereof as defined in any of claims 1 to 21 or with a pesticidally effective amount of an agricultural composition as defined in claim 27.
30. Seed, comprising at least one compound of formula (I) as defined in any of claims 1 to 21 and/or an agriculturally acceptable salt thereof.
31. A method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally effective amount of a compound of the formula (I) or a veterinally acceptable salt thereof as defined in any of claims 1 to 21.
32. Compounds of formula (I) and salts thereof
Figure imgf000120_0001
(I) wherein
Z is a group of the formulae (I I. A), (II. B) or (II. C)
Figure imgf000120_0002
(II.A) (II. B) (M C)
and wherein X, Y, R1, R2a, R2b, R2c, R2d, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, RZ1, T, m and n have the meanings given in any of claims 1 to 21 ;
except for compounds wherein n is 0, or n is 1 or 2 with RZ1 being Ci-Cβ-alkyl, Ci- Ce-alkoxy or halogen, Z is a group of formula (II.A) or (II. B) and R2a, R2b, R4a, R4b, R4c and R4d are all hydrogen.
33. Compounds of formula (I) and salts thereof
Figure imgf000121_0001
(I) wherein
Z is a group of the formulae (I I. A), (II. B) or (II. C)
Figure imgf000121_0002
(II.A) (II. B) (M C)
and wherein X, Y, R1, R2a, R2b, R2c, R2d, R3a, R3b, R3c, R3d, R4a, R4b, R4c, R4d, RZ1, T, m and n have the meanings given in any of claims 1 to 21 ;
except for compounds wherein n is 0 or n is 1 or 2 with RZ1 being Ci-Cβ-alkyl, Ci- Cβ-alkoxy, halogen, phenyl or naphthyl, and simultaneously Z is a group of formula (II.A) or (II. B), R2a, R2b, R3a, R3b, R3c and R3d are all hydrogen and one of R4a and R4b is hydrogen and the other is hydrogen or Ci-Cβ-alkyl and one of R4c and R4d is hydrogen and the other is hydrogen or Ci-Cβ-alkyl.
PCT/EP2008/056377 2007-05-25 2008-05-23 Aminoazoline and urea derivatives for combating animal pests WO2008145615A2 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102388059A (en) * 2009-02-11 2012-03-21 陶氏益农公司 Pesticidal compositions
CN102388058A (en) * 2009-02-11 2012-03-21 陶氏益农公司 Pesticidal compositions
WO2013186089A2 (en) 2012-06-14 2013-12-19 Basf Se Pesticidal methods using substituted 3-pyridyl thiazole compounds and derivatives for combating animal pests

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0251453A2 (en) * 1986-05-03 1988-01-07 Beecham Group Plc Substituted amino-dihydrooxazoles, -thiazoles and -imidazoles, process for their preparation and pharmaceutical compositions containing them
WO2007020377A2 (en) * 2005-08-15 2007-02-22 Syngenta Participations Ag Chemical compounds
EP1988080A1 (en) * 2007-05-03 2008-11-05 Bayer CropScience AG Insecticidal substituted 2-aminoindanes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0251453A2 (en) * 1986-05-03 1988-01-07 Beecham Group Plc Substituted amino-dihydrooxazoles, -thiazoles and -imidazoles, process for their preparation and pharmaceutical compositions containing them
WO2007020377A2 (en) * 2005-08-15 2007-02-22 Syngenta Participations Ag Chemical compounds
EP1988080A1 (en) * 2007-05-03 2008-11-05 Bayer CropScience AG Insecticidal substituted 2-aminoindanes

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102388059A (en) * 2009-02-11 2012-03-21 陶氏益农公司 Pesticidal compositions
CN102388058A (en) * 2009-02-11 2012-03-21 陶氏益农公司 Pesticidal compositions
CN102388058B (en) * 2009-02-11 2014-10-01 陶氏益农公司 Pesticidal compositions
CN102388059B (en) * 2009-02-11 2015-03-04 陶氏益农公司 Pesticidal compositions
WO2013186089A2 (en) 2012-06-14 2013-12-19 Basf Se Pesticidal methods using substituted 3-pyridyl thiazole compounds and derivatives for combating animal pests

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